Electrostatic information recording medium and electrostatic information recording and reproducing method

ABSTRACT

The present invention relates to an electrostatic information recording medium in which a charge retaining layer having high insulating properties is laminated on an electrode, and an electrostatic information recording/reproducing process wherein, while said electrostatic information recording medium is positioned in opposition to a photosensitive member on which a photoconductive layer is laminated, the recording medium is subjected to information exposure with the application of voltage between both electrodes to accumulate electrostatic charges thereon depending upon the dosage of said information exposure, and the electrostatic information thus accumulated is reproduced by potential reading. 
     The present electrostatic information recording medium has an information density as expressed in terms of a high recording capacity of the order of 8×10 8  bits/cm 2 , and makes it possible to process information in a planar state so that analog or digital information such as characters, line pictures, images, (0·1) information and sounds can be accumulated in the form of electrostatic charges. With the present electrostatic information recording medium, it is possible to obtain information of high quality and resolving power because of the information being accumulatable in electrostatic charge units. Due to its high charge retainability, it is further possible to store information permanently. Still further, it is possible to make inexpensive and simple recording/reproducing systems, since information can be output by reading local potentials of electrostatic latent images at any time and any scanning density.

This is a divisional of application Ser. No. 07/616,445, now U.S. Pat.No. 5,439,768 filed Nov. 20, 1990, which was a continuation-in-part ofSer. No. 07/353,084 filed on May 17, 1989, now abandoned.

BACKGROUND OF THE INVENTION

The present invention relates to an electrostatic information recordingmedium and an electrostatic information recording and reproducingmethod, by which the information can be electrostatically recorded andreproduced at any desired time.

Conventionally, silver salt photographing method is already known as atechnique for high sensitivity photographing. In this photographingmethod, the photographed image is recorded on film through thedevelopment process, and silver salt emulsion (such as photographicpaper) is used for reproducing the image or it is reproduced on cathoderay tube (CRT) by optically scanning the developed film.

There is also an electronic photographing technique, in which anelectrode is deposited on photoconductive layer by evaporation and thesurface of photoconductive layer is electrically charged by coronacharging in dark place. Then, it is exposed to intensive light to makethe exposed photoconductive layer electrically conductive. By removingthe electric charge on that portion by leaking it to form electrostaticlatent image on the surface of the photoconductive layer, and the toneris attached, which has electric charge with the polarity opposite tothat of the remaining electrostatic charge. This technique is mostlyused for duplication purpose and is not generally suitable forphotographing because of low sensitivity. Since electrostatic chargeretaining time is short, toner development is usually performed afterelectrostatic latent image is formed.

Further, there is the method for TV photographing technique, in whichphotographing is performed by the image pickup tube and the imageinformation obtained by optical semiconductor are taken out as electricsignal. This is directly outputted on CRT or is recorded on video bymagnetic recording and the image is reproduced on CRT when desired.

Also, a method is known, in which thermoplastic materials havingelectric charge carrying property are laminated on transparent electrodeand selenium particles are deposited by vacuum evaporation on thesurface of the thermoplastic material and is infiltrate to prepare therecording medium. To record the information on this recording medium,the surface of the thermoplastic material is electrically charged bycorona charging, and the image is exposed to light by applying voltagebetween the electrodes disposed at face-to-face positions. Thus, opticalcarrier is generated on the photoconductive particles in the exposureportion to form the latent image. For the development, the thermoplasticmaterial is softened by heating, and only the photoconductive particlesgenerating optical carrier are migrated in the thermoplastic materiallayer. The information thus developed are reproduced as visibleinformation according to the quantity of transmission light. (U.S. Pat.Nos. 3,520,681, 4,101,321 and 4,496,642).

Silver salt photographing method is an excellent means to preserve theimage of the object, but it requires a development process to form thesilver salt image and also the complicated optical, electrical andchemical processings are involved in reproducing the image to hard copyand soft copy (CRT output), etc.

The electronic photographing technique is more simple and quick than thesilver salt photographing method in reproducing the electrostatic latentimage, whereas the latent image can be preserved only for short period,and the dissociation of the development, image quality, etc. areinferior to those of silver salt method.

TV photographing technique requires linear sequential scanning to takeout and record the electric image signals obtained by the pickup tube.Linear sequential scanning is performed by electron beam in the pickuptube and by magnetic head in video recording. Since resolution dependsupon the number of scanning lines, it is extremely inferior to theplanar analog recording such as silver salt photographing.

The recently developed TV image pickup technique using solid-state imagesensor (such as CCD) is also essentially the same with regard to theresolution.

The problems involved in these techniques lie in the fact that theprocessing becomes more complicated if higher quality and resolution arerequired in the image recording and the memory function is lacking orimage quality is basically poor if the processing is simplified.

There is another technique, in which thermoplastic material layercontaining selenium particle layer is provided on the transparentelectrode and it is electrically charged by corona charging. After theimage is exposed, thermoplastic material is softened and the image isheat-developed, and the information are reproduced as visibleinformation. In this case, the electric charge information thusaccumulated can be preserved for long period (10 years or more), whereasthe application is limited as information recording means by camerabecause corona charging is needed for information recording. Also, onthe surface of thermoplastic resin softened during heat development, theso-called frost phenomenon occurs, in which fine irregularities arecaused by the repulsion between the surface electric charge, when it iselectrically charged to higher potential. As the result, when theaccumulated information are detected as surface potential, noise occursand the resolution is adversely affected.

SUMMARY OF THE INVENTION

The present invention is to solve the problems as described above, andit is to offer a new electrostatic information recording medium and anelectrostatic information recording and reproducing method, which canproduce the image of high quality at high resolution and the processingis simple and easy, whereby the recording can be achieved for long timeand the characters, line drawings, images, codes and (1, 0) informationcan be reproduced arbitrarily in appropriate quality.

Therefore, the first object of this invention is to provide anelectrostatic information recording medium having excellent chargeretainign property.

The second object of the present invention is to provide aphotosensitive member to be used for the electrostatic informationrecording and reproducing method, by which it is possible to usehigh-speed shutter, to discharge sufficiently even with slight incidentoptical image, to produce electrostatic latent image and to reproducecolor image.

Further, the third object of this invention is to offer an electrostaticinformation recording and reproducing method to reproduce theinformation accumulated on the electrostatic information recordingmedium as the electrostatic information.

The fourth object of this invention is to provide an electrostaticinformation recording medium, by which audio information can be recordedtogether with the characters, line drawings, codes and (1, 0)information.

The fifth object of the invention is to offer an electrostatic recordingcard of high quality and high resolution using the electrostaticinformation recording medium.

To meet the first object, the invention offers 7 types of electrostaticinformation recording medium as described below.

The first electrostatic information recording medium is characterized inthat the electric charge retaining layer with high insulating propertyis laminated on the electrode.

This electric charge retaining layer consists of macromolecular materialwith insulating property and is characterized in that the glasstransition temperature of said macromolecular material is higher thanthe environmental temperature and/or the water absorption ratio of saidmacromolecular material is 0.4 weight % or less.

The electric charge retaining layer must have the thickness of at least0.1 μm or more from the viewpoint of the insulating property and it ispreferably 100 μm or less from the viewpoint of flexibility.

The electric charge retaining layer of the electrostatic informationrecording medium must be composed of macromolecular material with highinsulating property in order to suppress the migration of electriccharge, and it must have specific resistance of 10¹² Ω·cm or more. Also,it is necessary the glass transition temperature of macromolecularmaterial constituting the electric charge retaining layer should behigher than the environmental temperature. The glass transitiontemperature is the temperature, at which the gradient of the decrease ofspecific volume when the molten macromolecular materials is cooled downshows discontinuous change. In general, macromolecular material has theglass transition temperature peculiar to its material property. Belowthe glass transition temperature, one segment of molecular chain cannotmigrate as a whole because heat energy is too low. On the other hand, ifit is above the glass transition temperature, heat energy is increasedand several or more atoms constituting the molecular chain can migrate,thus giving strong influence on specific heat, specific volume,toughness, brittleness temperature, etc.

Based on the innovative concept different from the conventional mode ofthinking, the present inventors have found that, in using the insulatingmaterial as the electrostatic information recording medium, it isnecessary to use it at less than the glass transition temperature tosuit the property of macromolecular materials constituting it.

In order to prevent the leakage of the information electric charge,which is accumulated as macromolecular materials constituting theelectric charge retaining layer, it is essential that water absorptionratio of macromolecular material is low. If water absorption ratio ishigher than 0.4 weight %, the resistivity is decreased by the influenceof moisture content adsorbed in the resin and this leads to poorinsulation. We also found that the electric charge retaining property islowered by the diffusion of electric charge toward the directions ofvolume and surface area.

The second electrostatic information recording medium is characterizedin that its electric charge retaining layer consists of mono layer orbuilt-up layers with insulating property.

The mono layer as used in the present invention must have specificresistance of 10¹² Ω·cm or more, and it is laminated on the electrode bythe well-known Langmuir-Blodgett's technique. The molecules in monolayer are arranged in such manner that molecular chains are regularlydisposed perpendicular to the electrode surface. Accordingly, theaccumulated electric charge does not permeate to the direction ofelectrode plane, and it is maintained in stable condition. In addition,the film is very thin and of sufficient strength suitable for the use asan electrostatic information recording medium.

The third electrostatic information recording medium is characterized inthat the electric charge retaining layer consists of light electret orthermal electret.

With the electric charge retaining layer consisting of electretmaterial, electric charge can be distributed and polarized by exposureto light under voltage application, and this contributes to thepermanent preservation of electrostatic information.

The fourth electrostatic information recording medium has the chargeretaining layer which may be the combination of the chargeretainability-reinforced layer and the thick insulating layer withoutelectric charge injection. It may be built up in such manner that ancharge retainability-reinforced layer is first formed on the electrode,and the thick insulating layer without electric charge injection is thenformed, or that thick insulating layer without electric charge injectionis first formed on the electrode, and then, the chargeretainability-reinforced layer is formed.

This charge retainability-reinforced layer is characterized in that itconsists of inorganic insulating film, organic macromolecular insulatingfilm, mono layer with organic insulating property or built-in layers,that its film thickness is within the range of 10-1000 Å, and that thethickness of the insulating layer without electric charge injection is100 Å or more.

By adjusting the material quality and film thickness of the chargeretainability-reinforced layer so that electric charge is migrated underhigh electric field, the information electric charge is migrated towardthe boundary surface with the insulating layer and it is preserved instable condition in the insulating layer without electric chargeinjection.

Further, the fifth electrostatic information recording medium ischaracterized in that its charge retaining layer consists of aninsulating resin layer containing conductive or photoconductiveparticles and electric charge is accumulated at said particles.

The photoconductive or electrically conductive particles are present atthe vicinity of the surface of the electric charge retaining layer assingle particle layers or multiple particle layers, or thephotoconductive or electrically conductive particles are dispersed inthe insulating resin layer and are laminated on the insulating resinlayer on the electrode. Or, the photoconductive or electricallyconductive particles are dispersed in the insulating resin layer and arelaminated on the electrode, and the information electric charge can bemaintained in stable condition in the insulating resin layer.

The sixth electrostatic information recording medium is characterized inthat its electric charge retaining layer consists of photoconductiveparticles or electrically conductive particles laminated in singlelayers or multiple layers, that the electric charge transport layershaving the function primarily to transport a part of electric charge aresequentially laminated on said particle layer and it is laminated on theelectrode from the side of insulating layer.

When the particle layer in this sixth electric charge retaining layerconsists of photoconductive particles, the information electric chargewith reverse polarity to transport carrier of the electric chargetransport layer is first formed on the surface, and the light with thewavelength to absorb the photoconductive particles is uniformlyirradiated. Then, both positive and negative carriers are generated onthe particle layer of the portion with the information electric charge,and the carrier with reverse polarity to that of the informationelectric charge accumulated on the surface moves the electric chargetransport layer and neutralizes the surface potential, and the electriccharge with the same polarity as that of the surface electric charge isaccumulated at the photoconductive particles as the information electriccharge. Also, the electric charge transport layer does not transport theelectric charge accumulated on the particle layer, and the electriccharge once accumulated will be permanently preserved.

When the particle layer consists of the electrically conductiveparticles, the electric charge on the surface of the electric chargetransport layer accumulated as described above is migrated toward theelectric charge transport layer without uniform exposure and isaccumulated at the conductive particle layer and is preservedpermanently on the conductive particle layer as the information electriccharge. The information electric charge thus accumulated is extremelystabilized because it is accumulated within the insulating layer.

The seventh electrostatic information recording medium is characterizedin that its electric charge retaining layer is laminated so that thephotoconductive layer is detachably laminated on the insulating layer,or the photoconductive layer remains laminated by etching thephotoconductive layer and by forming for each picture element. Or, thephotoconductive layer consists of the material with the orientation tothe direction of film thickness, or it consists of the photoconductiveparticle dispersion layer.

This electrostatic information recording medium is formed by disposingthe insulating layer and the photoconductive layer sequentially on theelectrode baseplate, whereas, unlike the information recording method tothe first-sixth electrostatic information recording media as describedabove, it is disposed at face-to-face position to the transparentelectrode instead of photosensitive member.

When information light is entered from the side of transparent electrodewith voltage applied between both electrodes, carrier is migrated towardthe electrode of electrostatic information recording medium in thephotoconductive layer, on which the information light is irradiated, andthe information electric charge is accumulated on the insulating layer.Although the photoconductive material constituting the photoconductivelayer has generally the insulating property, its electric chargeretaining property is low. Thus, the electric charge accumulated in thephotoconductive layer is migrated in the photoconductive layer as timeelapses. As the result, the phenomenon such as bleeding occurs on theimage when it is reproduced. The bleeding of the accumulated informationelectric charge can be prevented by detaching the photoconductive layerin the electrostatic information recording medium from the insulatinglayer at the stage when the information electric charge is accumulatedin the electric charge retaining layer. Also, bleeding can be preventedby performing etching on the photonductive layer for each pictureelement. Accordingly, the migration of electric charge in thephotoconductive layer can be prevented and the bleeding of thereproduced information can be avoided eitehr by forming thephotoconductive layer with the photoconductive material having theorientation toward the direction of film thickness or by forming thephotoconductive particles by the photoconductive particle dispersionmaterial with dispersed binder.

Next, description is given on the electrostatic information recordingand reproducing method according to the present invention. In theelectrostatic information recording apparatus, the photosensitive memberconsisting of photoconductive layer with electrode and the electrostaticinformation recording medium consisting of electric charge retaininglayer mounted on the electrode are provided in such manner that thesurface of photoconductive layer in the photosensitive member and thesurface of the electric charge retaining layer in the electrostaticinformation recording medium are disposed at face-to-face position. Thisphotosensitive member and the electrostatic information retaining mediummay be brought into direct contact or they may be disposed through aspacer on non-contact basis.

The photosensitive member to be used for the electrostatic informationrecording and reproducing method based on this invention ischaracterized in that an electrode is provided on the support member andthe photoconductive layer is laminated on said electrode.

When the information light enters from the side of photosensitivemember, it is better to have transparent support member and transparentelectrode. Or, light reflection preventive film may be laminated on theopposing surface where the electrode is furnished.

It is preferable that the discharge reinforced layer is laminated on thephotoconductive layer in the photosensitive member.

The photosensitive member is disposed at face-to-face position to theelectrostatic information recording medium, and it is used for theelectrostatic information recording and reproducing method with theincoming information light and under voltage application between bothelectrodes. It is provided with the function to discharge the electriccharge corresponding to the information light to the electrostaticinformation recording medium and to accumulate it by electric chargeinjection. It does not have the electrostatic charge retaining propertyby itself.

Therefore, it is preferable that the photosensitive member has theproperty to discharge at high sensitivity corresponding to theinformation light or to inject the electric charge. For example, whenthe discharge reinforced layer is furnished on the photoconductive layerof the photosensitive member, electrostatic latent image is formed atlow voltage and the effective external voltage can be reduced. Thismakes it possible to use the shutter at high speed. Even with weakincident light, the information electric charge is accumulated on theinsulating layer, and the responsiveness to light is also increased.Accordingly, it is possible to record the electrostatic image on theelectrostatic information recording medium at high sensitivity.

Further, a screen unit may be disposed in the optical path on a part ofthe photosensitive member, or a photoconductive layer cutaway portionmay be formed on a part of the electrode and the electrode may beexposed to said cutaway portion of the photoconductive layer. Or, ascreen unit may be furnished on a part of electrode, and the cutawayportion of the photoconductive layer may be formed on a part of saidelectrode. Or, the electrode may be exposed at the cutaway portion ofsaid photoconductive layer.

In the information light exposure and reproduction in the electrostaticinformation recording and reproducing method, the darkest value, i.e.fogging electric charge, can be determined and the exposure value can beadjusted by the electric charge formed on the corresponding electriccharge retaining layer when the screen unit is formed. Also, by forminga cutaway portion of photoconductive layer in the photosensitive memberand by disposing the electrode surface of the photosensitive memberdirectly to the electric charge retaining layer, the lightest value canbe recorded on the corresponding electric charge retaining layer. Thus,it is possible to adjust the amplification ratio in the informationreproduction and/or to use it as reference to the stability of theinformation potential accumulated on the electrostatic informationrecording medium as time elapses.

Also, it is possible to dispose a color filter on the support member ofthe photosensitive member or on the reflection preventive film. Thecolor filter may be a dyeing type color filter, a pigment type colorfilter, an inorganic interference type color filter, or a holographiccolor filter recording interference fringes of 3 primaries, and it canbe arranged as stripe type, plane division type, mosaic type, etc. Thecolor filter may be disposed separately from the support member or itmay be piled up on the support member.

Next, the recording method to the electrostatic information recordingmedium according to the invention will be described.

The recording method is characterized in that the information lightexposure is performed from the side of photosensitive member orelectrostatic information recording medium under voltage applicationbetween two electrodes.

There are the other methods such as the method to record using anelectrode needle head or an ion flow head or the method to accumulatethe information electric charge directly on the electrostaticinformation recording medium using optical printer such as laserprinter, but the preferable method is the electrostatic informationrecording method using the photosensitive member. In this case,electrostatic information can be recorded by disposing the surface ofthe electrostatic information recording medium at face-to-face positionto the surface of the photoconductive layer of the photosensitive memberon contact or non-contact basis.

In the fifth and sixth electrostatic information recording medium ofthis invention when photoconductive particles are contained, uniformexposure is performed on the electrostatic information recording mediumby the light with the wavelength to absorb the photoconductive particlesafter pattern exposure. Thus, it is possible to maintain theelectrostatic information at the particles and to keep the informationin stable condition.

The electrostatic information recording method on the seventhelectrostatic recording medium is performed by using transparentelectrode as photosensitive member.

On this seventh electrostatic information recording medium, voltage isapplied between transparent electrode and the electrode layer of theelectrostatic information recording medium with the medium and thetransparent electrode placed at face-to-face position, and informationexposure is performed. In this case, on the portion exposed to light ofthe photoconductive layer on the surface of the electrostaticinformation recording medium, photo carriers are generated in thephotoconductive layer, and resistance is decreased. The voltagedistributed to the photoconductive layer is redistributed to the air gapand to the insulating layer (electric charge retaining layer). As theresult, discharge occurs at the air gap according to Paschen's law, andthe electric charge in form of the image corresponding to the exposureintensity is accumulated on the surface between the insulating layer(electric charge retaining layer) and the photoconductive layer. In thiscase, if the photoconductive layer is continuous, i.e. it is continuousin lateral direction, the electric charge in form of the image isdiffused through the photoconductive layer, and electric charge image isdisturbed. This is because insulating property is still too low toretain electric charge for long period although the photoconductivelayer has insulating property in dark place. To avoid this, it may benecessary to detach the photoconductive layer, which causes thediffusion of electric charge after the image-like electric charge isrecorded, or to eliminate the lateral continuation of thephotoconductive layer in advance.

For this purpose, it is preferable that etching is performed at least onthe photoconductive layer on each independent unit in order to eliminatethe continuation in lateral direction. As the result, the electriccharge accumulated on the insulating layer (electric charge retaininglayer) can retain the image-like electric charge under the conditionthat one independant unit is turned to one pixel although diffusionoccurs within each independent unit. When the material having electriccharge retaining property as described in the present specification isused as the insulating layer (electric charge retaining layer), theimage-like electric charge is retained for long period, and it can beread at any time as potential.

In the following, description is given on the electrostatic informationrecording and reproducing method according to the present invention.

This invention is characterized in that the information recorded byelectrostatic information recording method is reproduced and outputtedas the electrostatic charge information.

In reproducing the recording, the potential difference from surfacepotential at the electrode and electrostatic information recordingmedium can be easily determined. For example, the generated potentialcan be detected by electric charge induced on the detection electrode.

A guard electrode may be furnished around the detection electrode, or aninsulating film may be provided on the surfaces of the detectionelectrode and the guard electrode.

Another method may be used, in which the detection electrode is a longthin rod type electrode and the distribution of the potential isdetermined by CT technique over the surface of the electrostaticinformation recording medium.

There is a further method, in which the detection electrode is disposedon the electrostatic information recording medium on contact ornon-contact basis and the accumulated electric charge is detected bypotential or current value.

Or, the potential of electric charge may be read by the method, in whichthe electrostatic information recording medium is processed by tonerdevelopment, the light beam is irradiated, and the reflected light isconverted photoelectrically.

In the electrostatic information recording and reproducing method basedon this invention, the electrostatic information is converted toposition information of the particles in the insulating layer and isrecorded, and a mixed layer consisting of the thermoplastic insulatingresin material and of the electric charge transport material totransport a part of electric charge is laminated, and thephotoconductive particle layer is disposed near the surface of thismixed layer in single or multiple layers.

In this case, the particles are migrated to the interior of theinsulating layer in accordance with the electric field strength by theaccumulated electrostatic information, and the electrostatic informationcan be converted to the position information and recorded. When thiselectrostatic information recording medium is used in the electrostaticinformation recording and reproducing method of this invention, thepotential generated on the surface of electric charge retaining layer atthe information recording is about 200 V. The frost phenomenon occursonly slightly on the surface of the insulating layer softened at thermaldevelopment. When the information is reproduced as electric chargepotential, the influence to the resolution by the irregularities of thesurface can be avoided, and the reproduction at high resolution can beachieved.

In the electrostatic information recording medium of the invention asdescribed above, the protective film may be arranged to increase theelectric charge retaining property.

The protective film may be the insulating plastic film or the filmproduced by coating of the insulating plastic solution, or the filmproduced by the melting transfer of the insulating melting plastics.

The electric charge recorded on the electrostatic information recordingmedium of this invention is gradually attenuated by moisture in the airor the like. Or, it may be destroyed by the damage from outside. Toprevent this, the surface of the electric charge retaining layer iscovered by the insulating coating to preserve the electrostaticinformation on the electrostatic information recording medium for longperiod.

In case no protective layer is furnished, electric charge is reduced ordisappears if the surface of the electric charge retaining layer isbrought into physical contact with the conductive material, whereas, ifprotective layer is provided, the surface potential is not reduced evenwhen the conductive material is brought into contact. When electrostaticcharge is generated on the surface of protective film by friction, itcan cleaned away easily with the conductive substance such as water, andthe electric charge can be protected. In reproducing the information,the protective film may be detached and the information electric chargeaccumulated on the electric charge retaining layer may be reproduced, orit can be reproduced through the protective film.

As described above, the electrostatic information recording medium ofthis invention can accumulate the analog information such as characters,line drawings, images, (0, 1) information, etc. or digital informationby making it an electric charge carrying layer with high charge carryingproperty. Thus, the information can be permanently preserved. Theinformation of high quality and high resolution can be accumulatedbecause the information is accumulated in electrostatic electric charge,and it can be preserved for long period as electrostatic latent image.

The information memory capacity in the electrostatic informationrecording medium of this invention is: 175 lines/in., 2R (4 pictureelements/mesh point), i.e. 350 picture elements/in.=14 dots/mm. Underthe condition of A4 size, it is: 297 mm×14 dots/in.×210 mm×14 dots/in.×4colors. The information quantity in the publication in A4 size is 50 MB,while the information quantity in 1 cm² of the electrostatic informationrecording medium of this invention is 1 μm×1 μm. If one picture elementshas 256 gradations (The information quantity of one picture element=1B)(analog recording), it is 1000 picture elements×1000 picture elementswith the information density of 1 MB/mm². Accordingly, for 1 cm² of theelectrostatic information recording medium, it is possible to enter theinformation as much as a color publication with 175 lines in A3 size.Compared with the information density of 3×10³ bit/cm² of a 8-inch 1 MBfloppy disk, 10⁶ bits/cm² of a high density floppy disk, 7.5×10⁶bits/cm² of a digital audio tape (DAT) and 2×10⁸ bits/cm² of anoptico-magnetic disk, the information density of the electrostaticinformation recording medium of this invention is as high as 8×10⁸bits/cm².

Because the accumulated information cna be obtained at any scanningdensity by reading and outputting the local potential of theelectrostatic latent image at any desired time, the image of high imagequality can be obtained in exactly the same way as in the silver saltphotographing and in reproducing it by optical scanning. Since physicalor chemical means such as the development means is not required for thedirect potential detection, inexpensive and convenient recording andreproducing system can be actualized.

In the electrostatic information recording medium of this invention,audio information can also be recorded at the same time.

A part of the information recording region of the electrostaticinformation recording medium is allocated for audio informationrecording, and audio information may be recorded. In the electrostaticinformation recording method of the invention, voice and sound can beconverted to optical information and recorded, and this audioinformation recording region is disposed on the periphery of theelectrostatic information recording medium. Accordingly, theelectrostatic information recording medium is provided with audioinformation recording region in addition to the information recordingregion for characters, line drawings, images, codes and (1, 0)information.

Also, the electrostatic information recording medium according to thepresent invention can be formed as an electrostatic informationrecording card by laminating it on the card base material such as theprepaid card, credit card, etc. In this case, the surface of theelectric charge retaining layer is exposed and embedded in the card basematerial or laminated by attaching on the card base material.

In laminating it on the card base material, it may be laminated on theelectrostatic information recording medium with or without the recordedinformation, or the recording form of information may be electric chargeor the toner by toner development. To record the information after it isformed in the form of a card, a part of the electrode of theelectrostatic information recording medium is to be exposed fromappropriate point of the card base material and to connect it with theelectrode of the photosensitive member. This makes it possible to recordthe information not only in case the medium with the recordedinformation is turned to the card form but also in case theelectrostatic recording medium without the recorded information isturned to the card form and the information can be recorded on it. Inthis case, protective film may be detachably laminated on the electriccharge retaining layer, or the protective film may be formed in thinfilm and recording may be made through the protective film. Especially,when digital information such as (0, 1) information is recorded byscanning through beam irradiation, the recorded electric charge can bepreserved as it is or by toner development, and it is possible todisplay it on CRT by the potential reading means or by the reproducingmeans or to output it on printer. Also, it is possible to utilize thereading means, which is used for optical card.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a cross-sectional view of the electrostatic informationrecording medium according to the present invention;

FIG. 2 is a perspective view of various types of flexible electrostaticinformation recording medium of this invention;

FIG. 3 is a cross-sectional view of the fourth electrostatic informationrecording medium of this invention;

FIG. 4 is a cross-sectional view of the fifth electrostatic informationrecording medium of this invention; FIG. 5 is a cross-sectional view ofthe sixth electrostatic information recording medium of this invention;

FIG. 6 is a cross-sectional view of the seventh electrostaticinformation recording medium of this invention;

FIG. 7 is a cross-sectional view of a photosensitive member in theelectrostatic information recording apparatus of this invention;

FIG. 8 and FIG. 9 are to explain another photosensitive member in theelectrostatic information recording apparatus of this invention;

FIG. 10 is a schematical drawing of the electrostatic informationrecording apparatus of this invention;

FIG. 11 is a drawing to show approximate configuration when theelectrostatic information recording apparatus is used as anelectrostatic camera;

FIG. 12 is a drawing giving the configuration of color-separatingoptical system;

FIG. 13 is an explanatory view of the case where color electrostaticlatent image is formed;

FIG. 14 is a drawing illustrating an example of the fine color filter;

FIG. 15 is a drawing showing an example, in which the fine color filterand a Fresnel lens are combined together;

FIG. 16 is a drawing giving 3-plane division by the simultaneous use ofND filter and the filters for R, G and B;

FIG. 17 is a drawing illustrating an embodiment of the manufacturingmethod of holographic color filter;

FIG. 18, FIG. 19 and FIG. 20 are the drawings showing the reproductionmethod of holographic color filter of FIG. 17;

FIG. 21 is a drawing illustrating another embodiment of the method toprepare the holographic color filter;

FIG. 22, FIG. 23 and FIG. 24 are the drawings showing the reproductionmethod of holographic color filter of FIG. 21;

FIG. 25 is a drawing illustrating the exposure method by divergent andconvergent lights;

FIG. 26 is a drawing illustrating a further embodiment of the method toprepare the holographic color filter;

FIG. 27 and FIG. 28 are the drawings illustrating the reproductionmethod of the holographic color filter prepared in FIG. 26;

FIG. 29 is a drawing showing an embodiment using Venetian blind;

FIG. 30 is a drawing giving another embodiment of the method to preparethe holographic color filter;

FIG. 31 is a drawing illustrating the reproduction method of holographiccolor filter of FIG. 30;

FIG. 32 is a drawing illustrating an example applying the electrostaticinformation recording and reproducing method of this invention;

FIG. 33 is a drawing to explain the electrostatic information recordingand reproducing method of this invention;

FIG. 34 is a drawing to explain the electrostatic information recordingmethod to thermal electret;

FIG. 35 is a drawing to explain the electrostatic information recordingmethod to optical electret;

FIG. 36 and FIG. 37 are the drawings to explain the electrostaticinformation recording method for the sixth electrostatic informationrecording medium of this invention;

FIG. 38 and FIG. 39 are the drawings to explain the informationrecording method to the electrostatic information recording mediumaccording to the present invention, in which the electrostaticinformation is converted to the position information;

FIG. 40 is a drawing to explain the information reproducing method inthe electrostatic information recording medium of this invention, inwhich the electrostatic information is converted to the positioninformation;

FIG. 41, FIG. 42 and FIG. 43 are the drawings to illustrate thepotential reading method of DC amplifying type;

FIG. 44, FIG. 45 and FIG. 46 are the drawings showing the examples ofthe potential reading method of AC amplifying type;

FIG. 47 and FIG. 48 are the drawings illustrating the examples of thepotential reading method by CT scanning method;

FIG. 49 is a drawing to give an example of the potential reading methodof power collecting type;

FIG. 50 is a drawing to show an example of the potential reading methodof electron beam type;

FIG. 51 and FIG. 52 are the drawings to explain the potential readingmethod utilizing the toner coloring;

FIG. 53 is a drawing to show approximate configuration of theelectrostatic image reproduction of this invention;

FIG. 54 is a schematical cross-sectional view of the electrostaticinformation recording medium equipped with protective film by thepresent invention;

FIG. 55 is a drawing to show the electrostatic information recordingmedium of the present invention, in which audio and image information isrecorded;

FIG. 56 and FIG. 57 are the drawings giving the memory region for theimage information and audio information;

FIG. 58 and FIG. 59 are the drawings illustrating the method to recordaudio information together with image information to the electrostaticinformation recording medium of this invention;

FIG. 60 is a drawing to illustrate another recording method using cyclicmemory;

FIG. 61 and FIG. 62 are the drawings to show theelectrostaticinformation recording card of this invention;

FIG. 63 is a drawing to explain the electrostatic information recordingmethod to the electrostatic information recording card of thisinvention;

FIG. 64 is a drawing to show the relationship between glass transitiontemperature and the electric charge carrying ratio when various types ofpolyester resin are used as electric charge carrying layer;

FIG. 65 is a drawing to explain the method to prepare a--Si: Hphotosensitive member;

FIG. 66 is a drawing to show electric charge carrying property of theelectrostatic information recording medium prepared by Example 10 (a),and

FIG. 67 is a drawing to show electric charge carrying property of theelectrostatic information recording medium with the protective filmprepared by Example 74.

DESCRIPTION OF THE PREFERRED EMBODIMENT

The first electrostatic information recording medium of the presentinvention will be explained in connection with FIG. 1.

The electric charge carrying layer 11 consists of macromolecularmaterial with high insulating property to suppress the migration ofelectric charge, and it must have specific resistance of 10¹² Ω·cm ormore.

As the macromolecular material to constitute the electric chargecarrying layer, it is essential that glass transition temperature ishigher than the operating environmental temperature, and it ispreferable that glass transition temperature is 20°-100° C. at normaloperating environment.

As the macromolecular material to constitute the electric chargeretaining layer, it is necessary that the water absorption ratio islower than 0.4% to prevent the leakage of the accumulated informationelectric charge by the influence of humidity.

As such macromolecular materials, thermoplastic resin, thermosettingresin, ultraviolet setting resin, electron beam setting resin orengineering plastics can be used.

As thermoplastic resin, the following compounds may be used:Polyethylene, vinyl chloride resin, polypropylene, styrene resin, ABSresin, polyvinyl alcohol, acryl resin, acrylonitrile-styrene resin,vinylidene chloride resin, AAS (ASA) resin, AES resin, cellulosederivative resin, thermoplastic polyurethane, polyvinyl-butyral,poly-4-methylpentene-1, polybutene-1, rosin ester resin, etc. Further,polyetheretherketone resin or polyparaxylylene expressed by thefollowing structural formulae can be used: ##STR1##

(C-type as described above may be, in addition to the compounds of theabove structure, the compounds, in which one of the sites other than themain chain bonding site in benzene ring is substituted by chlorine, orD-type may be the compound, in which two of such sites are substitutedby chlorine).

Also, fluorine-containing resin, e.g. fluororesin such aspoly-(tetrafluoroethylene) (PTFE),tetrafluoroethylene-perfluoroalkylvinylether copolymer (PFA),tetrafluoroethylene-hexafluoropropylene copolymer (FEP),tetrafluoroethylene-hexafluoropropylene-perfluoroalkylvinylethercopolymer (EPE), tetrafluoroethylene-ethylene copolymer (ETFE),poly-(chlorotrifluoroethylene) (PCTFE), chlorotrifluoroethyleneethylenecopolymer (ECTFE), etc. or thermoplastic resin, thermosetting resin orenergy beam setting resin such as ultraviolet setting resin, electronbeam setting resin, etc., engineering plastics, etc., in which hydrogenatoms are partially or totally substituted by fluorine atoms, orfluorine-containing resin may be mixed and used.

Or, fluorine-containing thermoplastic resin may be used, which hasmolecular weight with intrinsic viscosity of 0.1 at 50° C. and consistsof the repeating unit of cyclic structure given by a general formula:##STR2## and/or by a general formula: ##STR3## (where n is 1 or 2), orfluorine-containing thermoplastic resin may be used, which has molecularweight with intrinsic viscosity of 0.1 at 50° C. and consists of therepeating unit (a) expressed by a general formula: ##STR4## and/or by ageneral formula: ##STR5## (where n is 1 or 2) and by the repeating unit(b) given by a general formula:

    --(CF.sub.2 --CFX)--                                       (3)

(where X is F, Cl, --O--CF₂ CF₂ CF₃, --O--CF₂ CF(CF₃)OCF₂ CF₂ SO₃ F,--O--CF₂ CF₂ CF₂ COOCH₃) and containing at least the repeating unit (a)by 80 wt %.

The repeating unit (a) can be obtained by radical cyclic polymerizationof perfluoroallylvinylether or perfluorobutenylvinylether given by ageneral formula:

    CF.sub.2 ═CF--O--(CF.sub.2).sub.n CF═CF.sub.2

(where n is 1 or 2). Also, those containing the repeating unit (a) andthe above repeating unit (b) can be obtained by radical polymerizationwith perfluorovinylether given by a general formula:

    CF.sub.2 ═CF--O--(CF.sub.2).sub.n CF═CF.sub.2

(where n is 1 or 2) and the monomer given by a general formula:

    CF.sub.2 ═CFX

(where X is F, Cl, --O--CF₂ CF₂ CF₃, --O--CF₂ CF(CF₃)OCF₂ CF₂ SO₃ F,--O--CF₂ CF₂ CF₂ COOCH₃). These resins are described for example, by theJapanese Provisional Patent Publication No. 1-131215.

As thermosetting resin, the following compounds can be used: Unsaturatedpolyester resin, epoxy resin, phenol resin, urea resin, melamine resin,diallyl phthalate resin, silicone resin, etc.

As energy ray setting resins such as ultraviolet setting resin, electronbeam setting resin, etc., there are radical polymerized acrylatecompounds, e.g. ester compounds of acrylate, metacrylate or theirderivatives and having hydroxyl groups on both ends, e.g. hydroxyethylacrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethylmetacrylate, hydroxypropyl metacrylate, hydroxybutyl metacrylate,4-hydroxy-cyclohexyl acrylate, 5-hydroxy-cyclooctylacrylate,2-hydroxy-3-phenyloxypropyl acrylate, (meta) acrylic acid ester compoundhaving one polymerized unsaturated group, and the compound having twopolymerized unsaturated groups expressed by the following formula:##STR6##

As the setting compounds having two hydroxyl groups and one or two ormore radical polymerized unsaturated groups, glycerol metacrylate or theacrylates expressed by the formula: ##STR7## may be used. (Here, R andR' refer to methyl group or hydrogen, and R₁ to short-chain diolresidual group such as ethyleneglycol, propylene glycol,diethyleneglycol, butanediol, 1,6-hexanediol, etc.

As engineering plastics, polycarbonate, polyamide, acetal resin,polyphenyleneoxide, polybutylene terephthalate, polyethyleneterephthalate, polyethylene naphthalate, polyphenylene sulfide,polyimide resin, polysulfone, aromatic polyester, polyacrylate, etc. canbe used.

In the resins as described above with high water absorption ratio, theabsorption ratio can be decreased by introducing the atoms orsubstituents furnished with water non-absorbing property. Or, such resinmay be used by mixing with the resin with lower water absorption ratio.The materials with high water absorption ratio such as polyethersulfone, polyimide, polyparabanic acid, etc. can be used by laminatingthe protective film of the resin with lower water absorption ratio.

As the laminating method of electric charge retaining layer, there arethe methods to laminate the layers by depositing resin or rubber on theelectrode 13 by vacuum evaporation, by coating or dipping or bysputtering in case of electrostatic information recording medium asshown in FIG. 1 (a). In case the above cyclic polymer consisting of therepeating unit (a) given by the above general formula (1) and/or by (2)of copolymer consisting of the repeating unit (a) and the repeating unit(b) are used, it is preferable that fluorine type solvent such asperfluoro-(2-butyltetrahydrofuran), etc. is dissolved and coated.

For the electric charge retaining layer 11, silicon film, polyesterfilm, polyimide film, fluorine-containing polymer film, polyethylenefilm, polypropylene film, polyparabanic acid film, polycarbonate film,polyamide film, etc. may be bonded with bonding agent to form thelaminate layers. Or, the electrode layer may be formed on one side ofthe film by vacuum evaporation, sputtering or coating. In this case, thelayer to protect the electrode layer may be provided. If mechanicalstrength is required, the film or the like with higher mechanicalstrength may be bonded with it.

It is preferable that the thickness of the electric charge retaininglayer is 0.1-100 μm. If it is less than 0.1 μm, electric charge leakseven when electric charge is retained. If it is more than 100 μm,flexibility is lost when flexibility is needed.

The electrode 13 is laminated on the support member 15 as shown in FIG.1 (b) or on the support member 15 as shown in FIG. 1 (c) through thebonding layer 16, and there is no restriction of the material exceptthat it must have specific resistance of 10⁶ Ω·cm or less. It should beinorganic metal conductive film, inorganic metal oxide conductive film,or organic conductive film such as tertiary ammonium salt. Suchelectrode of electrostatic information recording medium is formed on thesupport member by various methods such as vacuum evaporation,sputtering, CVD, coating, metalplating, dipping, electrolyticpolymerization, etc. It is necessary to change the film thicknessaccording to electrical property constituting the electrode or by theapplied voltage at the recording of information. For example, it is100-3000 Å in case of aluminum, and it is determined according to thepattern of the total surface between the support member and the electriccharge retaining layer or to the pattern of the electric chargeretaining layer. As shown in FIG. 1 (a), the film may be laminated bythe same procedure as the electric charge retaining layer if theelectric charge retaining layer has a constant strength. The supportmember is not required in this case. Or, the electrode may be detachedafter the information has been recorded on the electric charge retaininglayer and it may be laminated again at the time of informationreproduction.

The support member 15 is to support the electrostatic informationrecording medium 3, and there is no restriction to its material andthickness, provided that it has the strength enough to support theelectric charge retaining layer. For example, flexible plastic film,metal foil, paper or rigid substances such as glass, plastic sheet,metal plate (also to be used as electrode) may be used, and lighttransmission property is also required. Actually, when the electrostaticinformation recording medium 3 takes the form of flexible film, tape ordisk, the flexible plastic film is used. In case higher strength isrequired, inorganic material with rigidity such as sheet, glass, etc.are used.

In case light transmission property is required, the anti-reflectionfilm may be provided or the film thickness of electrode layer orelectric charge retaining layer may be adjusted, or the reflectionprotective effect may be given by combining both.

The electrostatic information recording medium 3 is to record theinformation on the electric charge retaining layer 11 as thedistribution of electrostatic charge. Therefore, the electrostaticinformation recording medium may take various forms according to theinformation to be recorded or the recording method. For example, when itis used for electrostatic camera, it takes the form of normal film (forsingle frame or continuous frame) or disk. When digital information oranalog information is recorded by laser or the like, it takes the formof tape, disk or card.

In the following, description is given for the case where theelectrostatic information recording medium 3 takes the form of flexiblefilm, tape or disk. FIG. 2 (a) shows a type of the medium, in which therecording portion, i.e. the electric charge retaining layer 11, iscontinuous.

This is formed by providing the electric charge retaining layer on thesupport member such as plastic film equipped with the electrode layer,leaving only both edges of it. This electrostatic information recordingmedium has the length at least longer than that of one picture to berecorded (e.g. one frame in case of camera photographing, or track widthin case of digital information recording). Naturally, this includes thecombination or bonding of two or more electrostatic informationrecording media in longitudinal direction. In this case, there may be aslit zone between the adjacent electric charge retaining layers, wherethe retaining layer is partially lacking.

On the other hand, there is discontinuous type, as shown in FIG. 2 (b),where the electric charge retaining layer 11 is discontinuous inlongitudinal direction.

This is formed by providing the electric charge retaining layerdiscontinuously on the support member such as plastic film inlongitudinal direction, leaving both edges of the support member orwithout leaving them. On the support member, two or more electric chargeretaining layers are formed in a certain size. The size of the electriccharge retaining layer differs according to the image or the exposuremethod of the information input unit. In case of camera photographing,it is 35 mm×35 mm, and it is the track width of the digital informationrecording in case of the spot input such as laser beam. In case ofdigital information recording, the cutaway portion of the electriccharge retaining layer formed between the adjacent electric chargeretaining layers can be utilized as the tracking zone for input/outputof the information. Naturally, this includes the combination or bondingof two or more electrostatic information recording media in longitudinaldirection. In such case, there may be a slit zone between the adjacentelectric charge retaining layers, lacking a part of it.

As shown in FIG. 2 (c), there is the case where the electric chargeretaining layer is discontinuous to lateral direction.

In such case, the electric charge retaining layer is formeddiscontinuously in lateral direction on the support member such asplastic film equipped with electrode layer, leaving both edges of thesupport member or without leaving them. Thus, two or more band-likeelectric charge retaining layers are formed on the support member. Thewidth of the electric charge retaining layer is equal either to thetrack width of digital information to be recorded or to the widthmultiplied by integral number, and the cutaway portion of the electriccharge retaining layer formed between the adjacent electric chargeretaining layers is utilized as the tracking zone for input/output ofthe information.

As shown in FIG. 2 (d), there is also a disk type.

In this case, the electric charge retaining layer is provided totally onthe support member such as circular plastic film equipped with electrodelayer either totally or leaving spiral cutaway portion of continuousspiral electric charge retaining layer. In such electrostaticinformation recording medium, circular cutaway portion may be formed forthe driving of input/output device. In case of digital informationrecording, the cutaway portion of the electric charge retaining layer incontinuous and spiral form can be used as the tracking zone forinput/output of the information.

Next, description is given on the second electrostatic informationrecording medium of this invention.

In this case, the electric charge retaining layer of the electrostaticinformation recording medium is formed by single mono layer or built-uplayers.

Because LB film 11 is to record the information on its surface or in theinterior as the distribution of electrostatic charge, high insulatingproperty is required to suppress the migration of electric charge andmust have the insulating property of 10¹² Ω·cm or more in specificresistance.

As the organic compounds forming the mono layer or built-up layers, theorganic compounds capable to form LB film with specific resistance of10¹² Ω·cm or more, e.g. carbonic acids, amines, alcohols, siliconcompounds, phosphoric acid derivatives, sulfonic acids, cellulosederivatives, polymers, etc. can be used.

As the carbonic acids, for example, there are tetradecyl benzoate,2-nitro-5 (N-methyl) aminobenzoate, 2-nitro-5 (N-octadecyl)aminobenzoate, vinyl stearate, β-parinallic acid, trans-13-docosenoicacid, ω-tricosenic acid, glycine-octadecyl alcohol ester,2,4-octadecadienic acid, octadecyl fumaric acid, octadecyl maleic acid,ω-tricosenic acid, perfluorodecanic acid, perfluorononaic acid,perfluorooctanic acid, perfluoroheptanic acid, cartinonic acid,2-hexadecanic acid, n-octadecylacrylate, vinyl stearate, octadecylacrylate, glycine octadecyl ester, alamine octadecylester, 2-lysine, andthe substances having the following structural formulae: ##STR8##

Of the carbonic acids as described above, its salt also can be used ifthe substance is acid.

As the phosphate derivatives, the following substances can be used:Distearoyl-phosphatidyl-choline, dipalmitoyl-phosphatidylcholine,cholesterol, 1-palmitoyl-2-oleyl-SN-glycel-3-phosphacholine,L-α-dimyristyl-phosphatidic acid, L-α-dilauryl-phosphatidic acid,DL-α-dimyristoyl-phosphatidyl-ethanolamine,DL-α-dilauryl-phosphatidylcholine,DL-α-dipalmitoylnitrobenzoxadiazole-phosphatidylethanolamine,dioleoylphosphatidyl-choline, dipalmitoyl-lecithine,dimyristyl-lecithine, dipalmitoyl-phosphatidylethanolamine,dipalmitoyl-phasphatidylethanolamine, dipalmitoyl-phosphatidylcholineand the substances expressed by the following structural formula:

    CH.sub.3 (CH.sub.2).sub.17 OPO(OH).sub.3

As the cellulose derivatives, the following substances can be used:Cellulose triacetate, cellulose tricaprylate, cellulose tricaprate,cellulose trilaurate, cellulose dilaurate, and cellulose tripalmitate.As the polymers, there are: Poly-1-benzyl-L-histidine,poly-γ-benzyl-1-glutamate, polyoctadecyl-metacrylate,polyoctadecyl-acrylate, polymethyl-metacrylate,poly-γ-methyl-L-glutamate, polyimide, poly (n-octadecylvinylether/maleicacid anhydride), poly (octadecene-1/maleic acid anhydride), poly(styrene/maleic acid anhydride), poly-γ-methyl-L-glutamate, polystyrene,and the substances expressed by the following formulae: ##STR9##

As cyloxanes, the substances given by the following formulae can beused:

1 CH₃ (CH₂)₁₇ Si(Cl)₃

2 CH₃ (CH₂)₁₇ Si(OH)₃

3 CH₃ (CH₂)₇ CH═CH(CH₂)₇ Si(Cl)₃

4 CH₃ (CH₂)₇ CH═CH(CH₂)₇ Si(OH)₃

5 CH₃ OCO--(CH₂)₂₂ Si(Cl)₃

6 CH₃ OCO--(CH₂)₂₂ Si(OH)₃

Or the substances expressed by the following structural formula can beused: ##STR10##

In addition, the substances given by the following structural formulaecan be used: ##STR11## R and R' as described above are: wherein R═R',##STR12## Or, when R≠R', R is: ##STR13## R' is: --(CH₂)_(S) CONH C₂ H₅Or,

R is: ##STR14## R' is: --(CH₂)₂ CONH C₂ H₅ Or,

R is: ##STR15## R' is: ##STR16##

To form mono layer on the electrode surface, the solution of the abovecompounds in organic solvent is dropped onto water byLangmuir-Blodgett's method to deposit and form mono layer on aqueousphase. Thus, the following substances can be used: The substances formedby shifting the mono layer to the surface of clean electrode under theconstant superifical pressure when monomolecules are lined up along theinterface, the substances formed by immersion of electrode plate in thesolution such as silane coupling agent already known and used forchemical combination of organic polymer and inorganic material, and thesubstances formed by the known means to form mono layer film such as thedeposition of organic compounds on the surface of the electrode and theadsorption of the mono layer. The thickness of mono layer is the size ofthe constituent molecule, i.e. about 20-100 Å. In case of built-uplayer, the layers thickness is a multiple of the thickness of mono layercorresponding to the cumulative frequency.

In forming the mono layer or built-up layers by LB method, it is formed,for example, by general means as described in "The New ExperimentalChemistry Course: Vol. 18; Interface and Colloids", pp. 498-507(Maruzen). As the method to align monomolecules in the built-up layers,there are the method to adsorb the lipophilic group on electrodesurface, the method to adsorb the hydrophilic group on electrodesurface, or the method to laminate on these monomolecular films from theside of lipophilic group or from hydrophilic group (the so-called, X, Yor Z-type).

The above polymers without hydrophilic group can be formed by placing LBfilm on the baseplate. In case of polystyrene, for instance, it isdropped on water surface and mono layer is formed, and the attachedbaseplate is brought into contact with water surface in parallel.

In the following, description is given on the third electrostaticinformation recording medium of this invention.

As the electrostatic charge recording method, there is the electret toprovide the distribution of electric charge and polarization inside theinsulating medium in addition to the so-called free electric chargerecording method to accumulate the surface electric charge as describedabove.

In the optical electret, the electrode is formed on the support membersuch as film, and ZnS, CdS, ZnO, etc. are furnished on the electrodeplate with each layer of 1-5 μm by vacuum evaporation, sputtering, CVD,coating, etc., and the electrode is laid upon this photosensitive layeron contact or non-contact basis.

As the materials for thermal electret, there are polyvinylidene fluoride(PVDF), poly (VDF/ethylene trifluoride), poly (VDF/ethylenetetrafluoride), polyvinyl fluoride, polyvinylidene chloride,poly-acrylonitrile, poly-α-chloroacrylonitrile, poly(acrylonitrile/vinyl chloride), polyamide 11, polyamide 3,poly-m-phenylene-isophthalamide, polycarbonate, poly (vinylidenecyanidevinyl acetate), PVDF/PZT complex, etc., and the material is furnished onthe electrode baseplate in single layer of 1-50 μm or two or morematerials are laminated.

The fourth electrostatic information recording medium of this inventionis described in connection with FIG. 3.

The electric charge retainability reinforced layer 10 of theelectrostatic information recording medium consists of inorganicinsulating film, organic mono insulating layer, organic insulating monolayer or built-up layers with film thickness within the range of 10-1000Å. It should have such film thickness and material quality that theinformation electric charge accumulated by electrode or discharge goesinto it by the action of the electric field generated by the informationelectric charge. The insulating layer 11 without electric chargeinjection is formed by the insulating material and must have filmthickness of 100 Å or more, and it should have such film thickness ormaterial quality that the information electric charge does not go intoit by the action of the electric field generated by the informationelectric charge.

The electric charge retainability reinforced layer 10 is defined as thelayer, into which electric charge enters when strong electric field (10⁴V/cm or more) is applied but it does not enter when low electric field(less than 10⁴ V/cm) is applied. As the electric charge retainabilityreinforced layer, SiO₂, Al₂ O₃, SiC, SiN, etc. can be used. As organicsubstances, polyethylene vacuum-deposited film or polyparaxylylenevacuum-evaporated film can be used. Also, as organic insulatingmonomolecular film or monomolecular built-up film, aromatic compoundswith specific resistance of 10¹² Ω·cm or more, e.g. carbonic acidderivatives of styrene, ω-phenylic acid, or cadmium arachidiate, arelaminated in 1-10 layers by Langmuir-Blodgett's technique and used.

In order to stabilize the electrostatic charge, it is preferable to addthe substance having electron donating property (donor material) or thesubstance with electron accepting property (acceptor material) to theinsulating layer 11 without electric charge injection. As donormaterials, there are the compounds such as styrene, pyrene, naphthalene,anthracene, pyridine, azine, etc. Actually, the compounds such astetrafluvalene (TTF), polyvinylpyridine, polyvinylnaphthalene,polyvinylanthracene, polyazine, polyvinylpyrene, polystyrene, etc. areused in single compound or in mixture. As the acceptor materials, thereare halogen compounds, cyanide compounds, nitro compounds, etc.Actually, the compounds such as tetracyanoquinodimethane (TCNQ),trinitrofluorenone (TNF), etc. are used in single compound or inmixture. Donor material or acceptor material is added to resin by about0.001-10%.

In order to stabilize the electrostatic charge, single element particlesmay be added to the insulating layer. As the single element, thefollowing elements are used: I A group (alkali metals), I B group(copper group), II A group (alkali earth metals), II B group (zincgroup), III A group (aluminum group), III B group (rare earth group), IVB (titanium group), V B group (vanadium group), VI B group (chromiumgroup), VII B group (managanese group), VIII group (iron group andplatinum group), or silicon, germanium, tin, lead as IV A group (carbongroup), antimony, bismuth as V A group (nitrogen group), sulfur,selenium and tellurium as VI A group (oxygen group). These are used infine powder. Of the elements as described above, the metals can be usedin the forms of metallic ions, fine powder alloy, organic metal orcomplex. Further, the above elements can be used in the forms of oxides,phosphates, sulfonated compounds or halogenated compounds. Theseadditives may be added in small quantity to the electrostaticinformation recording medium made of resin, rubber, etc., and the addedquantity may be 0.01-10 weight % to the electrostatic informationrecording medium.

The insulating layer must have the thickness of at least 1000 Å (0.1 μm)from the viewpoint of insulation and less than 100 μm from the viewpointof flexibility.

Next, description is given on the fifth electrostatic informationrecording medium of this invention.

The particles to store the electric charge are composed ofphotoconductive materials and the electrically conductive materials. Asthe materials for the photoconductive particles, there are inorganicphotoconductive materials such as amorphous silicon, crystal silicon,amorphous selenium, crystal selenium, cadmium sulfide, zinc oxides, andorganic photoconductive materials such as polyvinylcarbazole,phthalocyanine, azo pigment, etc. or triphenylmethane, pyrylium salt,xanthene or basic dyes are used.

As the electrically conductive materials, the following elements areused in fine powder: I A group (alkali metals) in periodic table, I Bgroup (copper group), II A group (alkali earth metals), II B group (zincgroup), III A group (aluminum group), III B group (rare earth metals),IV B group (titanium group), V B group (vanadium group), VI B group(chromium group), VII B group (manganese group), VIII group (iron groupand platinum group), carbon, silicon, germanium, tin and lead as IV Agroup (carbon group), antimony and bismuth as V A group (nitrogengroup), and sulfur, selenium and tellurium as VI A group (oxygen group).

Of the above elements, the metals can be used in the form of fine powderalloy, organic metal or complex. Further, they can be used in the formof oxides, phosphates, sulfonated compounds or halogenated compounds.Above all, carbon, gold, copper, aluminum, etc. are preferably used.

Next, the method to form the particle layer is described.

First, the electrostatic information recording medium as shown in FIG. 4(a) is formed by depositing the particle layer forming materials on theresin layer 11, which is in unhardened molten or softened conditions andis laminated on the support member, by means of a vacuum evaporationunit of low vacuum.

When vaporized under low vacuum condition of 10 Torr-10⁻³ Torr, theparticle layer forming material is aggregated and is turned to fineparticles of 10-0.1 μm. If the resin layer is softened by heating duringvacuum evaporation, the particles 12 are laminated in arrangedconditions in single layer or multiple layers. If the resin layer ismade of thermoplastic resin, the resin layer is softened by heating theelectrode layer by resistance heating or it is softened by directlyheating the baseplate by heater. If the resin layer is made ofthermosetting resin, ultraviolet setting resin or electron beam settingresin, the particle layer forming material is deposited by vacuumevaporation in the unhardened condition and it is hardened byappropriate hardening means after the particle layer is formed.

There is another method to form the fine particle layer in the vicinityof the interior surface of the resin layer. By this method, the particlelayers 12 are deposited on the support member, which is formed byhardening said resin layer on the electrode baseplate in advance, insingle layer or in multiple layers by vacuum evaporation. In this case,the particle layer is formed in the vicinity of the interior surface ofthe resin layer. Then, the same resin as the resin used for theformation of said resin layer or the different insulating resin islaminated within the range of 0.1 μm-30 μm. As the laminating methods,there are the dry methods such as vacuum evaporation or sputtering todirectly form the resin layer, or the wet methods, by which, resin isfirst dissolved by solvent, and, after forming the film by spinnercoating, dipping, blade coating, etc., the solvent is dried up. Toensure the uniform particle size during the formation of the particlelayer, the baseplate may be heated up to the temperature, at which theresin layer is not melted.

The resin layer 11 and the particle layer 12 are sequentially laminatedon the support member as shown in FIG. 4 (b). To attain this, theparticle layer forming material in fine particles is dispersed in theresin layer forming material by adding the suitable hardening agent andsolvent, and this is coated on the resin layer 11, formed on the supportmember in advance, by coating and dipping.

Further, the material to form the particle layer 12 in fine particles isdispersed in the resin layer 11 as shown in FIG. 4 (c). To form this,the particle layer forming material is dispersed in the resin layerforming material by adding the suitable hardening agent and solvent andby coating it on the support member by coating and dipping.

Next, description is given on the sixth electrostatic informationrecording medium of this invention.

The sixth electrostatic information recording medium is characterized inthat the electric charge transport layer 19 is laminated on the electriccharge retaining layer of the fifth electrostatic information recordingmedium as described above as shown in FIG. 5.

The electric charge transport layer 19 is provided with the function toprimarily transport the electric charge on one side. As the materials toform the hole transport layer, the electric charge transport materialcan be used, which is formed by dispersing the following substances intoresin: Amorphous silicon, amorphous selenium doped with B, Al, Ga, In,etc. or oxadiazole, pyrazoline, hydrazone, polyvinylcarbazole, stilbene,anthracene, naphthalene, tridiphenyl-methane, triphenylmethane, azine,amine, aromatic amine, etc.

As the materials to form the electron transport layer, the followingsubstances can be used: Amorphous silicon doped with P, N, As, Sb, Bi,etc. or ZnO, polyvinylcarbazole-trinitrofluorene electric chargemigration complex.

To laminate the electric charge transport material, there is the drymethod to form the electric charge transport layer directly on the fineparticle layer by vacuum evaporation, sputtering method, etc. or the wetmethod to dissolve or suspend the photoconductive material in solventand, after forming the film by spinner coating method, the solvent isdried up. The material may be laminated with the thickness of 0.5 μm-50μm. If film thickness is less than 0.5 μm, the accumulated informationelectric charge may be adversely affected by the trouble such as theapproach of the opposite electric charge to the surface of theelectrostatic image recording medium. If film thickness is 50 μm ormore, trouble may be caused in reproducing the information.

Next, the seventh electrostatic information recording medium of thisinvention is described.

When light is irradiated on the photoconductive layer laminated on theinsulating layer, optical carriers (electrons and positive holes) aregenerated on the irradiated portion. When the conductive layer has suchwidth as to facilitate the migration of these carriers or when anelectric field is present, the effects are especially conspicuous. Thematerials are composed of inorganic photoconductive materials, organicphotoconductive materials, organic and inorganic composite typephotoconductive materials, etc.

The photoconductive layer 9 is laminated on the insulating layer 11 asshown in FIG. 6 (a). This is formed by coating the inorganicphotoconductive material, organic photoconductive material or organicand inorganic composite type photoconductive material by coating, vacuumevaporation, sputtering or CVD method.

The medium having the picture elements 24 as shown in FIG. 6 (b) isformed by sequentially laminating the electrostatic informationrecording medium electrode 13, the insulating layer 11, photoconductivelayer 9 on the support member 15 of the insulating layer. After theresist pattern for each picture element is formed on the photoconductivelayer by photo resist, etching is performed on the photoconductive layerunder acidic or alkaline atmosphere.

There are various etching methods. Because one unit obtained by etchingis turned to one pixel, the resolution of the image is determined by itsfineness. Therefore, it is desirable to perform as fine etching aspossible and to have finer unit.

As a method to provide fine etching, there is photolithography usingresist. After pattern exposure is performed using resist, there are theprocesses of resist development, etching and removing. As the etchingmethods, there are a method to use alkaline or acidic chemical solutionor to perform dry etching under the atmosphere of oxygen or fluorinetype gas in plasma. As the exposure method to resist, there is a methodto directly draw by electron beam or to use X-ray.

As the photoconductive material, for which etching is achievable, it ispreferable to use inorganic materials among the materials as describedin the present specification, such as amorphous silicon, amorphousselenium, cadmium sulfide, zinc oxide, etc. Above all, amorphous siliconor amorphous selenium, for which etching can be performed, aredesirable.

In case amorphous silicon is used, it is possible to control p-typehaving excellent hole transporting property or n-type having excellentelectron transporting property by doping. Dopant gives no influence toetching because it is used in very small quantity, while it is necessaryto take the polarity of the applied voltage into account when voltageapplication or image exposure is performed. Doping may be performed foramorphous selenium to improve spectral sensitivity or heat-resistantproperty, but there is no problem also in this case.

On the other hand, if the fineness of pixel unit does not become anissue, one unit can be formed by masking when photoconductive film isdeposited by dry or wet method. In addition, there are various methodsto form one unit, whereas any method may be used if fine fabrication canbe achieved.

Also, it is possible to give orientation to the photoconductive layer 9as shown in FIG. 6 (c). To form this, cadmium sulfide (CdS), zinc oxide(ZnO), etc. are used as photoconductive material, and it is piled up onthe insulating layer in argon plasma using CdS or ZnO as target. Then,the film with crystal orientation oriented toward the direction of filmthickness can be obtained by selecting the sputtering conditions.

Further, as shown in FIG. 6 (d), the photoconductive layer 9 is obtainedas follows: The particles of cadmium sulfide (CdS) or zinc oxide (ZnO)(particle size: 1-100 μm) are dispersed in the binder. Then, by addingthe solvent and by coating it on the baseplate, the photoconductivelayer with dispersed photoconductive particles can be obtained.

The electrostatic information recording and reproducing or playing-backprocesses according to the present invention will not be explained.

Basically, the electrophotographic information recording system used tothis end comprises an electrostatic information recording medium and aphotosensitive member located in opposition thereto.

Upon irradiated with light, a photoconductive layer 9 forming aphotosensitive member 1, as shown in FIG. 7, generates light carriers(electrons, positive holes) from the irradiated region, which canmigrate widthwisely therethrough. The layer 9 is more effective esp. inthe presence of an electric field. The layer 9 may be formed of aninorganic photoconductive material, an organic photoconductive material,a composite type of inorganic/organic photoconductive material thereofand so on.

Such photoconductive materials and the formation of the photoconductivelayers will now be explained.

(A) Inorganic Photosensitive Member (Photoconductor)

Inorganic photosensitive materials used may include amorphous silicon,amorphous selenium, cadmium sulfide, zinc oxide and so on.

(a) Amorphous Silicon Photosensitive Member

The amorphous silicon photosensitive member may be formed of:

(i) Hydrogenated amorphous silicon (a--Si:H), and

(ii) Fluorinated amorphous silicon (a--Si:F) which

is not doped with impurities, is doped with B, Al, Ga, In, Tl or thelike into a p-type (a hole transfer type), or is doped with P, Ag, Sb,Bi or the like into an n-type (an electron transfer type).

For the formation of a photosensitive layer, silane and impurity gasesmay be introduced with a hydrogen gas, etc. into a low vacuum atmosphere(10⁻² to 1 Torr) to deposit them on an electrode substrate heated or notheated by glow discharge into a film, or may be formed on a simplyheated electrode substrate through thermochemical reactions.Alternatively, the starting solid material may be formed into a film byvapor deposition or sputtering. The obtained film may be used in theform of a single or laminated layers. The film may have a thickness of 1to 50 μm.

A transparent electrode 7 may be provided on its surface with a chargeblocking layer which, when not exposed to light, serves to preventcharges from being injected from the transparent electrode 7, as ifexposed to light. For that purpose, an insulating layer or layers suchas a--SiN, a--SiC, SiO₂ and Al₂ O₃ layers may be formed on one or bothof the electrode substrate and the uppermost (surface) layer of thephotosensitive member by glow discharge, vapor deposition, sputtering orother suitable means. The insulating layer(s) is (are) required to havea thickness of at least 3000 Å or below, since too an increasedthickness prevents charges formed by exposure from passing through theinsulating layer, with the result that they are accumulated in thephotosensitive member in the form of space charges. It is preferred thatthe insulating layer(s) has (have) a thickness of 100 to 1000 Å byreason that it (they) is (are) then easy to prepare.

Preferably, the electrode substrate may be formed as the charge blockinglayer with a charge transport layer capable of transporting charges ofpolarity opposite to that of the electrode substrate, making use of arectifying effect. If the electrode is negative, a hole transport layermay then be provided, and if the electrode is positive, an electrontransport layer may then be provided. For instance, a--Si:H (n⁺) whereinSi is doped with boron has hole transport properties so increased thatit produces a rectifying effect, and so functions as a negative chargeblocking layer.

(b) Amorphous Selenium Photosensitive Member

Photosensitive amorphous selenium includes (i) amorphous selenium(a--Se), (ii) amorphous selenium tellurium (a--Se--Te), (iii) amorphousarsenic selenium (a--As--Se), (iv) amorphous arsenic selenium Te(a--As--Se--Te) or the like.

This photosensitive film may be prepared by vapor deposition orsputtering, and an SiO₂, Al₂ O₃, SiC or SiN layer may be formed on anelectrode substrate as the charge blocking layer by vapor deposition,sputtering, glow discharge or other suitable means. Alternatively, theabove substances (i) to (iv) may be used in combination and form ed intoa laminated type of photosensitive member. The photosensitive member mayhave a similar film thickness as stated in connection with the amorphoussilicon photosensitive member.

(c) Cadmium Sulfide (CdS)

This photosensitive member may be prepared by coating, vapor depositionor sputtering. For vapor deposition, solid particles of CdS may beplaced on a tungsten boat and vapor-deposited thereon by resistanceheating or EB (electron beams). For sputtering, a CdS target may be usedto deposite on a substrate in argon plasma. In this case, CdS is usuallydeposited in an amorphous state, but it may be possible to obtain acrystalline oriented film (oriented in the thickness direction) byselecting the conditions for sputtering. For coating, CdS particles(having a particle size of 1 to 100 μm) dispersed in a binder with theaddition of a solvent may be coated on a substrate.

(d) Zinc Oxide (ZnO)

This photosensitive member may be prepared by coating or CVD. Forcoating, ZnO particles (having a particle size of 1 to 100 μm) dispersedin a binder with the addition of a solvent may be coated on a substrate.For CVD, an organic metal such as diethyl zinc or dimethyl zinc is mixedwith an oxygen gas in low vacuum (10⁻² to 1 Torr) and subjected tochemical reactions on an electrode substrate heated (to 150° to 400°C.), whereby it is deposited thereon in the form of a zinc oxide film,which is again oriented in the thickness direction.

(B) Organic Photosensitive Member

The organic photosensitive member is broken down into single-layer andfunction-separated types.

(a) Single Layer Type of Photosensitive Member

The single layer type of photosensitive member comprises a mixture of acharge generator substance with a charge transporter substance.

Charge Generators!

The charge generators are substances having the property of absorbinglight to generate charges and transmitting such charges to the chargetransporter substances. Used to this end are substances based on azopigments, bis-azo pigments, trisazo pigments, phthalocyanine pigments,perylene pigments, triphenylmethane dyes, styryl dyes, azulenium saltpigments, squalenium salt pigments, methine pigments, pyrylium dyes,cyanine dyes and methine dyes.

Charge Transporters!

The charge transporters are substances capable of satisfactorilytransporting ionized charges. Used to this end are substances based onhydrazones, pyrazolines, polyvinyl carbazoles, carbazoles, stilbenes,anthracenes, naphthalenes, tridiphenylmethanes, azines, amines, aromaticamines, oxadiazoles, triazoles, polycyclic aromatics and the like.

A charge-transfer complex may also be formed from the charge-generatingand transporting substances.

Usually, photosensitive members have their photosensitivecharacteristics determined by the light absorption properties of thecharge-generating substances. However, the complexes obtained by mixingthe charge generating substances with the charge transporting substanceshave their light absorption properties varied. For instance, polyvinylcarbazole (PVK) is only sensitive in an ultraviolet region andtrinitrofluorenone (TNF) is only sensitive in the vicinity of a 400-nmwavelength region, but a PVK-TNF complex is sensitive even to wavelengthregions of up to 650 nm.

Preferably, such a single layer type of photosensitive member has a filmthickness of 10 to 50 μm.

(b) Function-Separated Type of Photosensitive Member

The charge-generating substances tend to absorb light to generatecharges but have the property of trapping charges, whereas thecharge-transporting substances have superior charge-transportingcharacteristics but are inferior in the charge-generating properties dueto light absorption. For that reason, both the substances are separatedfrom each other to make much use of their individual properties. Acharge generating layer is thus laminated on a charge transportinglayer, and vice versa.

In order to make the function-separated type of photosensitive member,the charge-generating substance is first dissolved or dispersed with abinder in a solvent and the resulting coating solution is spread on anelectrode to form a charge generating layer. Then, the chargetransporting substance is likewise dissolved or dispersed with a binderin a solvent and the resulting coating solution is spread and then driedon the charge generating layer to form a charge transporting layer.Preferably, the charge generating layer may have a film thickness of 0.1to 10 μm, while the charge transporting layer may be of 10 to 50 μm infilm thickness.

Binders used for both the single-layer and function-separated types oforganic photosensitive members may include, for instance, siliconeresins, styrene/butadiene copolymer resins, epoxy resins, acrylicresins, saturated or unsaturated polyester resins, polycarbonate resins,polyvinyl acetal resins, phenolic resins, polymethyl methacrylate (PMMA)resins, melamine resins and polyimide resins. For facilitateddeposition, the binder may be used in an amount of 0.1 to 10 parts perpart of each of the charge-generating and transporting layers. Forcoating, use may be made of dipping, vapor deposition, sputtering orother suitable means.

(c) Inorganic/Organic Laminated Type of Photosensitive Layer

The member may be formed (1) using the above inorganic photoconductivelayer such as a--Si, a--Se, CdS and ZnO layers for the charge generatinglayer and the above organic charge transporting layer for the chargetransporting layer or (2) using the above organic charge generatinglayer for the charge generating layer and the above inorganicphotoconductive layer for the charge transporting layer.

Referring to the film thickness, the charge-generating and transportinglayers may be 0.1 to 10 μm and 10 to 50 μm, respectively, as is the casewith the above function-separated type of organic photosensitive member.

The charge blocking layer will now be explained in more detail.

The charge blocking layer may be provided to prevent a dark current fromoccurring on at least one or both sides of the photoconductive layer 9(the injection of charges from the electrode) at the time when voltageis applied, viz., a phenomenon where, as if exposed to light, chargesmigrate through the photoconductor even when not actually exposed tolight.

The charge blocking layer is of two types, one making use of a so-calledphenomenon where charge transfer occurs in the presence of a highelectric field and the other the rectifying effect. With the layermaking use of such a phenomenon a current does neither pass through thephotoconductive layer nor reach the surface of the insulating layer.When light is incident upon that layer, however, a high electric fieldis applied to its region on which light is incident due to the presenceof one (electron or hole) of charges generated in the photoconductivelayer, so that a current can pass through the charge blocking layerthrough the resulting charge transfer effect. Such a charge blockinglayer may be formed of an inorganic insulating film, an organicinsulating polymeric film, an insulating mono layer and so on, which maybe used alone or laminated. The inorganic insulating film may beobtained from As₂ O₃, B₂ O₃, Bi₂ O₃, CdS, CaO, CeO₂, Cr₂ O₃, CoO, GeO₂,HfO₂, Fe₂ O₃, La₂ O₃, MgO, MnO₂, Nd₂ O₃, Nb₂ O₅, PbO, Sb₂ O₃, SiO₂,SeO₂, Ta₂ O₅, TiO₂, WO₃, V₂ O₅, Y₂ O₅, Y₂ O₃, ZrO₂, BaTiO₃, Al₂ O₃, Bi₂TiO₅, CaO--SrO, CaO--Y₂ O₃, Cr--SiO, LiTaO₃, PbTiO₃, PbZrO₃, ZrO₂ --CO,ZrO₂ --SiO₂, AlN, BN, NbN, Si₃ N₄, TaN, TiN, VN, ZrN, SiC, TiC, WC, Al₄C₃ and so on by glow discharge, vapor deposition, sputtering or othersuitable means. It is noted that the thickness of this film may bedetermined for each material, while taking into consideration theinsulating properties for preventing the injection of charges and thecharge transfer effect. For the charge injection-preventing layer makinguse of the rectifying effect, there is provided a charge transportinglayer capable of transporting charges and having polarity opposite tothat of the electrode substrate. Thus, such a chargeinjection-preventing layer is formed of an inorganic photoconductivelayer, an organic photoconductive layer or a composite inorganic/organictype of photoconductive layer, and has a film thickness of about 0.1 to10 μm. More specifically, when the electrode is negative, use may bemade of an amorphous silicon photoconductive layer doped with B, Al, Ga,In and so on as well as an organic photoconductive layer obtained bydispersing throughout resins amorphous selenium or oxadiazole,pyrazoline, polyvinyl carbazole, stilbene, anthracene, naphthalene,tridiphenylmethane, triphenylethane, azine, amine, aromatic amine or thelike. When the electrode is positive, use may be made of an amorphoussilicon photoconductive layer doped with P, N, As, Sb, Bi or the like aswell as a ZnO photoconductive layer or the like formed by glowdischarge, vapor deposition, CVD, coating or other suitable means.

The photosensitive member used in the present invention is alsocharacterized in that a discharge-reinforcing layer 2 in the form of afilm is formed on the above photoconductive layer 9, as illustrated inFIG. 8.

As the discharge-reinforcing materials, use may be made of metalcompounds of high electron emissivity such as BaO, CaO, SrO, MgO, CeB₆,CsSb, Sb--Rb--Cs, Ag--O--Cs, W--Th, TiC, TiO, Y₂ O₃, La₂ O₃, Dy₂ O₃ andThO₂ or metal oxides.

The discharge-reinforcing layer 2 may be formed on the surface of thephotoconductive layer 9 by conventional film-forming techniques such asvapor deposition, sputtering, plasma CVD or coating using a binder, andhave a film thickness of preferably 50 to 5000 Å, more preferably 100 to1000 Å.

The electrode 7 is provided on a support 5, except that the support isformed of a metal, and may be formed of any material having a specificresistance value of 10⁶ Ω·cm or below. Usable to this end are, e.g., aninorganic metal film, an inorganic metal oxide film or an organic filmsuch as a quarternary ammonium salt film, all being electricallyconductive. Such an electrode 7 may be formed on the support 5 by vapordeposition, sputtering, CVD, coating, plating, dipping, electrolyticpolymerization or other suitable means. The thickness of the electrode 7has to be varied depending upon the electrical properties of thematerial forming it and the voltage to be applied for recordinginformation, but may be on the order of 100 to 3000 Å where it is formedof aluminium, for instance. As is the case with the photoconductivelayer support 5, the electrode 7 is required to have such opticalproperties as mentioned above, when it is necessary forinformation-bearing light to be incident thereon. For instance, if theinformation-bearing light is visible light (400 to 700 nm), use may thenbe made of transparent electrodes obtained by the vapor deposition orsputtering of, e.g., ITO (In₂ O₃ --SnO₂) or SnO₂ or the coating offinely divided powders thereof formed with a binder into an ink,semi-transparent electrodes obtained by the vapor deposition orsputtering of, e.g., Au, Al, Ag, Ni or Cr, or organic transparentelectrodes obtained by the coating of, e.g., tetracyanoquinodimethane(TCNQ) or polyacetylene.

The above electrode material may also be used in the case where theinformation-bearing light is infrared light (700 nm or more). In somecases, a colored electrode capable of absorbing visible light may beused so as to cut off visible light.

Basically, the above electrode material may be also used in the casewhere the information-bearing light is ultraviolet light (400 nm orbelow). However, an electrode substrate material absorbing ultravioletlight (such as an organic polymeric material and soda glass) isunpreferred. Thus, preferable is a material such as quartz glass, whichcan transmit ultraviolet light therethrough.

No particular limitation is imposed on the material and thickness of thesupport 5 of the photosensitive member, as long as it has strengthsufficient to support the photosensitive member. For instance, use maybe made of flexible plastic films, metal foils, paper, glass, plasticsheets or rigid materials such as metal sheets (which may also serve aselectrodes). However, when the support is used for a system forrecording information with light incident from the photosensitivemember, it is essentially required to transmit that light. For thesupport employed with a camera using natural light incident from thephotosensitive member, use may be made of a transparent sheet or plasticfilm or sheet, all having a thickness of about 1 mm.

Where the support is required to be transparent to light incident fromthe photosensitive member for information recording, a anti-reflectionlayer may be provided thereon and/or the thickness of the electrodelayer or the photoconductive layer may be adjusted, thereby achievingthe desired anti-reflection effect.

Next, description is given by FIG. 9 on the photosensitive member usedfor correcting the electrostatic information potential to be recorded onthe electrostatic information recording medium.

In the figure, 1 is a photosensitive member, 3 an electrostaticinformation recording medium, 151 an exposed portion, 153 a non-exposedportion, 155 an illuminating light source, 157 and 160 are lightscreening unit, 159 a non-transparent electrode unit, and 161 a lackingportion of photoconductive layer.

In the electrostatic information recording method of this invention,information exposure is performed with voltage applied between thephotosensitive member and the electrode of the electrostatic informationrecording medium, and the potential distribution corresponding to theexposure intensity as given in FIG. 9 (b) occurs on the electrostaticinformation recording medium. When exposure intensity is increased, thispotential is raised, while there is maximum potential, which issaturated at more than the predetermined value and defined by supplyvoltage. On the contrary, if exposure intensity is decreased, thepotential is also decreased, whereas it is not ultimately turned to 0.Dark current flows between two electrodes even when not exposed, andthere is minimum potential based on this. Even when maximum potentialand minimum potential are generated on the electric charge retainingmedium and are used as reference potential and exposure is performedbetween the exposure quantity C and D in FIG. 9 (b), it is possible onthe photosensitive member of this invention to correct the imagepotential according to this potential.

FIG. 9 (a) shows the exposed portion 151 where maximum potential isgenerated and the non-exposed portion 153 where minimum potential isgenerated on the electrostatic information recording medium 3.

First, description is given on the photosensitive member used to formthe exposed portion 151 in FIG. 9 (a) in connection with FIGS. 9(c)-(e).

In FIG. 9 (c) a part of the electrode 7 of the photosensitive member 1is bent to form the exposed portion 7a so that exposure is performed onthe surface of the photoconductive layer placed face-to-face to theelectrostatic information recording medium. When information exposure isperformed with the photosensitive member and the electrostaticinformation recording medium at face-to-face position, maximum electricfield locally determined by supply voltage is applied on the region ofthe electrostatic information recording medium opposing to the exposedportion 7a of the electrode, and electric charge is accumulated on theopposing electrostatic information recording medium to reach the maximumpotential.

In FIG. 9 (d), an exposed portion 7b of the electrode is formed, on thesurface of photoconductive layer by increasing the thickness of a partof the electrode, and maximum potential is generated as in the case of(c).

In FIG. 9 (e), a part of the photosensitive member 1 is removed bymasking, etching, solvent, etc. to expose the electrode 7d. In thiscase, unlike the cases of (c) and (d), it is necessary to correct inadvance the difference of maximum potential on the electrostaticinformation recording medium caused by the difference of gap distanceaccording to Paschen's law on discharge.

Next, description is given on the method to form the non-exposed portion153 in connection with FIGS. 9 (f)-(i).

In FIG. 9 (f), a light screening unit 157 is masked on the surface ofthe electrode support member. When such photosensitive member is placedface-to-face to the electrostatic information recording medium andexposure is performed, the portion facing to the light screening unit157 is not exposed to light, and minimum potential corresponding locallyto dark current is generated on the electrostatic information recordingmedium.

In FIG. 9 (g), a part of the transparent electrode is masked by aluminumto make it non-transparent, and minimum potential is generated as inFIG. 9 (f).

In FIG. 9 (h), non-transparent portion is formed on a part of thesupport member by aluminum vapor deposition and transparent electrode isevaporated on it, and minimum potential is generated as in the case ofFIGS. 9 (f) and (g). In this case, it is necessary to decrease the filmthickness obtained by vapor deposition in comparison with the thicknessof the photosensitive member.

In FIG. 9 (i), a portion 161 lacking photoconductive property, i.e.non-photoconductive portion, is formed on a part of the photoconductivelayer so that carriers are not generated even when irradiated by light.On the non-photoconductive portion, the carrier injection from theelectrode occurs in the same degree as on the photoconductive layer indark state. The transport property of the injected carriers occurs inthe same degree as on the photoconductive layer in dark state. Anymaterial can be used if it is not photoconductive to wavelength of thelight for exposure. In other words, any material will do if it gives thesame effect as the photoconductive layer in non-exposed state even whenit is exposed to light. As an example such material, PVK/TNF may be usedas the photoconductive layer, or PVK is used as non-photoconductiveportion, or the portion not containing electric charge generating agenton a part of electric charge generation layer is furnished on thefunction-separated type photosensitive member, where electric chargegeneration layer and the electric charge transport layer are laminated,to provide non-photoconductive portion. Also, it is possible to useinsulating polymer material with adjusted resistance value.

When it is supposed that maximum potential and minimum potential on theelectrostatic information recording medium are A and B respectively asgiven in FIG. 9 (b) in case the exposed portion and the non-exposedportion are provided using such photosensitive member, the potential ofthe portion where the image is recorded will take the value between Aand B. The fluctuation of initial image voltage caused by the propertyof photosensitive member, thickness, applied voltage, and environmentalconditions can be easily corrected if the potential on the exposedportion and the non-exposed portion is measured. In case the imagepotential is decreased due to the changes over time, the potential onthe exposed portion and the non-exposed portion is also attenuated.Therefore, the potential of the exposed portion can be easily correctedby measuring the potential on the exposed portion and the non-exposedportion in advance. The above description has been given on an examplewhere both the exposed portion and the non-exposed portion are provided,whereas one of them will suffice.

In the electrostatic information recording system according to thepresent invention, a photosensitive member 1 is laminated on aelectrostatic information recording medium 3 in opposite relationthrough or not through a spacer 28, as illustrated in FIG. 10. With avoltage impression type of switch (not shown), charges are accumulatedon the insulating layer depending upon the quantity of incident light toform an incident optical image on the charge-retaining layer.

Where the spacer is used, the space between the photosensitive memberand the electrostatic information recording medium is suitably in arange of 1 to 50 μm. The spacer may be formed of an organic materialsuch as plastics or an inorganic material such as glass and laminated inplace with an insulating solvent such as silicone oil.

Referring to possible exposure manners, planar exposure may basically beapplied. However, scanning exposure recording may also be possible with,e.g., laser. For laser recording systems, argon laser (514, 488 nm),helium-neon laser (633 nm) or semiconductor laser (780 nm, 810 nm, etc.)may be used as the light sources. Voltage is then applied with thephotosensitive member being brought in close planar contact with or inopposition to the electrostatic information recording medium at aconstant interval. In this case, the electrode may be of the samepolarity as that of the carrier of the photosensitive member. In thatstate, laser exposure corresponding to picture image, character, cord orline signals is carried out by scanning. Analog recording forinformation such as picture images is carried out by the modulation ofthe light intensity of laser, while digital recording for characters,cords or line pictures is effected by the on-off control of laser beams.Dotted imaging may also be carried out under the dot generator on-offcontrol of laser beams. It is noted that the spectral properties of thephotoconductive layer in the photosensitive member need not bepanchromatic, and may be sensitive to the wavelength of the laser beamsource.

A schematic view of an electrostatic camera to which the electrostaticinformation recording system of the present invention is applied isillustrated in FIG. 11, in which reference numerals common to FIG. 10stand for like parts. It is noted that reference numeral 21 denotes aphotographing lens, 23 a mirror, 25 a forcusing screen, 27 a pentagonalprism, 29 an eye lens and 30 a negative image.

In this electrostatic camera, the photosensitive member 1 andelectrostatic information recording medium 3, shown in FIG. 1, are usedin place of films for signel-lens reflex cameras. Upon a power source 17put on or off with a switch not shown, the mirror 23 is jumped up to aposition shown by a dotted line to form an electrostatic latent image ofa subject on the electrostatic information recording medium 3. Ifrequired, the toner development of the electrostatic informationrecording medium gives the negative image 30. The electrostaticpotential may also be read to produce electrical signals for display onCRT₃ or recording on other recording medium such as magnetic tapes.

Next, description is given on the method to form color image using colorfilter.

A prismatically optical system for color separation is illustrated inFIG. 12 (a), wherein reference numerals 71, 73 and 75 stand for prisms,77, 79 and 81 filters and 83 and 85 reflectors.

The prismatically optical system for color separation comprises threeprismatic blocks. Optical information incident from a plane a of theprismatic block 71 is partly separated and reflected from a plane b andthen reflected from the plane a to obtain an optical component of Bcolor through the filter 77. The rest of the optical information isincident on the prismatic block 73 and reaches a plane c from which itis partly separated and reflected. Another portion reaches directly thefilters 79 and 81 from which optical components of G and R colors areobtained. The optical components of G and B colors may then be reflectedfrom the reflectors 83 and 85 to obtain the R, G and B light componentsin the form of parallel light beams.

FIG. 12 (b) is a schematical drawing of a 3-plane division opticalsystem, in which Pr and Pb represent prisms, Mr and Mb represent totalreflection planes, Dr and Db represent dichroic mirrors, and Ir, Ib andIg are image forming planes.

Now, description is given on 3-plane division optical system. The prismPr has a total reflection plane Mr and is furnished in an optical pathof blue light. Dichroic mirror Db is provided in good balance with thetotal reflection plane Mb and reflects blue light and transmits redlight and green light. The dichroic mirror Dr is provided in goodbalance with the total reflection plane Mr, reflects red light, andtransmits green light and blue light. By extending the optical path ofred light by prism Pr and the optical path of blue light by prism Pb,the optical image of red color component of the object, formed on theimage forming plate Ir, and the optical image of blue color component ofthe object, formed on the image forming plane Ib, are formed on the sameplane as the optical image of green color component of the object,formed on the image forming plate Ig, in form of a straight line at thepositions closer to each other.

By disposing such a filter 91 in front of the photosensitive member 1for photographing as illustrated in FIG. 13 (a), one frame may be formedeither by three sets of electrostatic information recording mediaseparated into the R, G and B colors, as shown in FIG. 13 (b), or by aset of R, G and B images formed on one plane, as illustrated in FIG. 13(c).

Description is now given on color filter.

FIG. 14 is a fine color filter. For instance, this may be formed, e.g.,by exposing a resist-coated film to light through a mask pattern to formstriped patterns of R, G and B, which are then dyed in R, G and B;passing the light components separated with the system of FIG. 12through fine slits to obtain interference fringes of R, G and B, whichare then recorded in a hologram recording medium; or exposing aphotoconductor to light while a mask is brought in close contacttherewith to form striped patterns of R, G and B defined byelectrostatic latent images, which are then toner-developed andtransferred three times for color compounding, thereby forming tonerstripes. In the filter formed as mentioned just above, a set of R, G andB forms one picture element as fine as about 10 μm. If this filter isused as the filter 91 of FIG. 13, it is then possible to form anelectrostatic latent image broken down into colors. In this case, thefilter may be spaced away from or made integrate with the photosensitivemember.

FIG. 15 is a view showing an example of a combination of the fine colorfilter with a Fresnel lens, in which patterns R, G and B can be reducedin size by the Fresnel lens for recording and a lens design may be mademore compact and thinner than conventional lens designs.

FIG. 16 is a view showing an example of three-plane splitting in whichan ND (natural density) filter is used in combination with R, G and Bfilters. Indicent light is split into three portions through ND filters81 and 83 and a reflector 85, which are then allowed to pass through anR filter 87, a G filter 89 and a B filter 91 to obtain R, G and Bcomponents of light as parallel light beams.

Also, it is possible to use normal holographic color filter as colorfilter. For example, a filter can used, by which interference fringesare formed and recorded by irradiating two beams consisting ofmonochromatic light to the photosensitive material from the same side orfrom opposite side and on which interference fringes are recorded tothat the diffraction wavelength by two beams is turned to 3 primarycolors by providing a mask on one side of the photosensitive materialand by deviating the mask position sequentially. Further, 3 primarycolors may be recorded by using the light of the same wavelength and bychanging the thickness of the photosensitive material by chemicalprocessing before or after the exposure.

In this case, at least one of two beams irradiated from the same sidesor from the opposite sides may be irradiated diagonally to thephotosensitive material.

Further, the interference fringes where diffracwavelength of two beamsbecomes 3 primary colors may be recorded by changing the irradiationangle to the photosensitive material for each exposure without using themask, or two beams may be a combination of divergent light andconvergent light.

According to this holographic color filter, when two beams of each of 3primary colors are irradiated from the opposite side of thephotosensitive material, of which a mask is disposed on one side andinterference fringes are formed and recorded, the primary diffractionlight of R, G and B is obtained during reproduction, and the light of C,M and Y is obtained as transmission light. The light of R, G and B canform the image on off-line basis by releasing it in lateral directionusing half mirror or by inclining the irradiation angle of the lightduring exposure. Also, when interference fringes are formed and recordedby irradiating 3 primary colors to the same photosensitive materialthrough mask from the same side to the photosensitive material, thelight of R, G and B can be obtained as the transmission primarydiffraction light, and only the light of the predetermined direction canbe selected by simultaneously using venetian blind. The primarydiffraction light can be obtained in different direction for each of 3primary colors through the formation of interference fringes byirradiating at different angles for each of 3 primary colors. Theholographic color filter thus formed can be easily manufactured becausesingle development process will suffice. This results in low costproduction, and the diffraction light of pure color can be obtained.

Now, description is given on the method to form such holographic colorfilter and the application to the electrostatic information recordingand reproducing method.

FIGS. 17 and 18 are views showing one embodiment of the holographiccolor filter, in which reference numeral 41 stands for a photosensitivematerial, 42 a mask, 43 and 44 monochromatic light beams, 45 aphotosensitive material and 46 a lens.

As illustrated in FIG. 17, the mask 42 slitted, e.g., in the stripedform is positioned in place on both sides of the photosensitive material41, which is then irradiated with monochromatic light, e.g., R lightfrom the opposite directions to record an interference pattern due tothe R light. Then, interference patterns are recorded in superposedrelation by G light with the mask 42 displaced by a given distance andthen B light with the mask 42 similarly displaced by a given distance.Subsequent development of the interference patterns thus subjected totriple exposure gives a color hologram.

Then, while the formed color hologram 41 is brought in close contactwith the photosensitive material 45, it is irradiated with light throughthe lens 46 from the opposite direction, as illustrated in FIG. 18.Thereupon, the reflected light beams of R, G and B are obtained asregenerated light beams, while the transmitted light beams of C, M and Yare obtained as the complementary colors of R, G and B. Obtained in thiscase is a striped color filter in which one picture element is definedby R, G and B.

In the instant embodiment, only one development is need for each R, Gand B. And, since R, G and B are in principle subjected to totalreflection with no possibility of color mixing, it is possible to obtainthe transmitted light beams of pure C, M and Y and use the holographiccolor filter at 100% efficiency.

FIG. 19 is a view showing another embodiment. Throughout FIGS. 17-19,the same parts are indicated by the same reference numerals. It isnoted, however, that 47 and 48 stand for a half mirror and a lens,respectively.

In the instant embodiment, a holographic color filter is prepared in asimilar manner as illustrated in FIG. 17 to make use of R, G and B lightcomponents appearing on the incident side.

The R, G and B light components, which appear on the incident side,cannot be used as such. For that reason, they are guided sideways by thehalf mirror 4 and condensed for use. More exactly, upon light strikingupon the hologram 41 through the lens 46, R, G and B light componentsare reflected from the hologram 41 and then the half mirror 47 to formR, G and B images on the photosensitive material 45 under the condensingaction of the lens. It is here to be noted that the lens 48 is used forcondensing purposes, since the photosensitive material 45 cannot bebrought in close contact with the film, unlike the system of FIG. 18.

FIGS. 20 and 21 are views showing still another embodiment. ThroughoutFIGS. 19 to 21, like reference numerals stand for like parts.

In the embodiment of FIG. 19, the use of the half mirror 47 leads tolight losses, so that the resulting images tend to become dim. In theinstand embodiment, therefore, one monochromatic light is caused to beobliquely incident so as to form a hologram. Upon light striking upon aholographic color filter comprising this hologram, R, G and B lightcomponents are reflected therefrom at angles. Hece, the R, G and B lightcomponents are deflected sideways for focusing on the photosensitivematerial 45.

FIGS. 22 and 23 are views illustrating a further embodiment, whereineach of R, G and B is exposed to light to form a holographic colorfilter.

As illustrated in FIGS. 23 (a), (b) and (c), a holographic color filteris subjected to triple exposure with R light, G light and B light. Asillustrated, this holographic color filter is then irradiated with thelight through a lens 46, whereby R, G and B images can be formed on anoff-line. In other words, the R, G and B images are reflected indifferent directions, as shown in FIG. 14, whereby they can be formed onthe respective photosensitive materials 45a, 45b and 45c.

It is understood that in the exposure system of FIG. 23, monochromaticlight diverging from a point P may be focused on a point Q by theinterference of monochromatic light condensing at the point P with themonochromatic light diverging from the point Q, as illustrated in FIG.25 (a). It is thus possible to form the R, G and B images on thephotosensitive materials 45a, 45b and 45c in a lensless manner byvarying the point Q for each R, G and B light to form interferencefringes as illustrated in FIG. 25 (a), whereby the filter is irradiatedwith the light diverging from the point P, as shown in FIG. 25 (b).

With a system of such a structure as illustrated in FIG. 25, a lenslikeaction can be imparted to a holographic color filter. When thisholographic color filter is applied to the electrostatic informationrecording and reproducing processes of the present invention, it ispossible to increase the dosage per unit area and condense light withhigh resolution, thus making high-quality recording possible. Theforegoing refers to a reflection type of holographic color filter. Inwhat follows, reference will now be made to a transmission type ofholographic color filter.

As illustrated in FIG. 26, monochromatic light beams 43 and 44 arecaused to be incident on a photosensitive material 41 with the givenangles being made therebetween. With a mask 42 displaced for each R, Gand B, interference fringes are recorded in the photosensitive material41 to form a holographic color filter.

FIG. 27 is a view showing an example of the thus prepared transmissiontype of holographic color filter making use of zero-order light.

In the instant embodiment, primary diffracted light beams of R, G and Bare generated in the same direction as the incident light 43, so thatzero-order light beams of C, M and Y are obtained as transmitted lightbeams, which may then be focused on a photosensitive material 45 to forma color image.

FIG. 28 is a view showing a further embodiment of the present invention,wherein the primary diffracted light beams of R, G and B of FIG. 27 aredesigned to be focused on a photosensitive material 45 through a lens48.

FIG. 29 is a view showing a further embodiment of the present inventionusing a Venetian blind, wherein a holographic color filter 41, aVenetian blind 50 and a photosensitive material 45 are brought in closecontact with one another to make use of diffracted light in apredetermined direction. The Venetian blind 50 is only transparent tolight in its crystal direction and serves to select only zero-ordertransmitted light or primary diffracted light to form an image definedby such light on the photosensitive material 45.

FIG. 30 is a view showing a further embodiment wherein a photosensitivematerial 41 is subjected to triple exposure with monochromatic lightbeams of R, G and B from the same direction, as shown in FIGS. 30 (a),30 (b) and 30 (c). In this case, the angles of both beams of eachmonochromatic light are varied, as illustrated in FIG. 31, whereby thetransmitted primary diffracted light components of R, G and B areseparated during the irradiation of light.

FIG. 32 is a view illustrating the application of a holographic colorfilter to the electrostatic information recording and reproducingprocesses of the present invention. If the photosensitive member 1 isexposed to light through this holographic color filter, it is thenpossible to increase the dosage per unit area and hence obtainsufficient brightness, and conduct color exposure of high resolutionwith the application of voltage.

Reference will now be made to the electrostatic information recordingprocess according to the present invention.

This process is illustrated in FIG. 33 in which reference numeral 1denotes a photosensitive member 1, 3 an electrostatic informationrecording medium, 5 a support, 7 an electrode, 9 a photoconductivelayer, 11 a charge retaining layer (an insulating layer), 13 anelectrode, 15 a support and 17 a power source.

In the embodiment of FIG. 33, exposure is carried out from thephotosensitive member 1. The photoconductive layer support 5 formed of 1mm thick glass is first provided thereon with the transparent electrode7 formed of 1000 Å thick ITO, on which the photoconductive layer 9 ofabout 10 μm in thickness is formed to obtain the photosensitivemember 1. With respect to this photosensitive member 1, theelectrostatic information recording medium 3 is arranged through a gapof about 10 μm. The electrostatic information recording medium 3 isobtained by the vapor deposition of an aluminium electrode of 1000 Å inthickness on the insulating layer support 15 formed of 1 mm thick glass,followed by the formation of a 10 μm thick charge retaining layer (aninsulating layer) on that electrode.

As illustrated in FIG. 33 (a), the recording medium 3 is first arrangedwith respect to the photosensitive member 1 through a gap of about 10μm. Then, voltage is applied from the power source 17 between theelectrodes 7 and 13, as illustrated in FIG. 33 (c). Since thephotoconductive layer 9 is a high resistor in a dark place, no changetakes place between the electrodes, if the voltage applied to the gap islower than the firing voltage according to the Paschen's law. As avoltage higher than the firing voltage is applied to the gap from anexternal power source, discharge occurs to build up charges on thesurface of the electrostatic information recording medium and that statecontinues until the firing voltage is reached, thus resulting in abackground potential. When light 18 is incident from the photosensitivemember 1, a portion of the photoconductive layer 9, on which the lightstrikes, is made so electrically conductive that discharge takes placethrough the air layer to accumulate charges on the electrostaticinformation recording medium. If microparticles of photoconductivity andelectrical conductivity are incorporated in the charge retaining layer,information-bearing charges migrate into such microparticles by anelectric field defined by the built-up charges and, optionally, byexposure, and are then stabilized in the insulating layer. Even whenthere are previously uniform background charges further accumulation ofcharges takes place on the portion of the photoconductive layer 9 onwhich the light strikes. After the completion of the exposure, thevoltage is shut off as illustrated in FIG. 33 (c), and the electrostaticinformation recording medium 3 is then removed out, whereby theformation of an electrostatic latent image is completed.

The photosensitive member 1 may be brought in contact (as mentionedabove) or no contact with the electrostatic information recording medium3. In the contact type system, positive or negative charges are injectedfrom the electrode 7 of the photosensitive member into the portion ofthe photoconductive layer 9 exposed to light. While attracted by theelectrode 13, the injected charges pass through the photoconductivelayer 9 and reach the surface of the insulating layer 11 where they stopand are accumulated. Then, with the photosensitive member 1 separatedfrom the electrostatic information recording medium 3, the insulatinglayer 11 is separated while the charges remain accumulated thereon.

The voltage applied and exposure time are arbitrarily determined wherethe quantity of incident light is in proportion to the amount of chargetransfer and before the amount of charge transfer is saturated. In thepresent invention, however, it is preferred that a voltage of 100 V to2000 V is applied as a voltage shutter for 10⁻⁶ to 10 seconds so as toachieve electrostatic recording of high sensitivity. With the first andsecond electrostatic recording media, electrostatic information may berecorded in this manner.

In order to record information in a photoelectret that is the thirdelectrostatic information recording medium, a transparent electrode 40is superposed on the surface of a phtosensitive layer of the electret incontact or non-contact relationship, as shown in FIG. 34 (a). Uponexposed to light with the application of voltage as shown in FIG. 34(b), charges are generated by light from the exposed region andpolarized by an electric field. Even when the electric field is removedoff, the charges remain trapped in that position, as illustrated in FIG.34 (c). Thus, an electret corresponding to the dosage is obtained. It isnoted that this electrostatic information recording medium isadvantageous in that any separate photosensitive member is not needed.

In order to record information in a thermoelectret, it is heated to atemperature higher than the glass transition temperature of the materialforming it by resistance heating or other suitable means prior toexposure, as shown in FIG. 35. In that state, the electret is exposed tolight with the application of voltage, as illustrated in FIG. 35 (b). Athigh temperatures, the mobility of ions is so increased that a highelectric field is applied to an insulating layer in the exposed region.Of the thermally activated ions, negative and positive charges areattracted to the positive and negative electrodes, respectively, therebyforming space charges for polarization. Subsequent cooling of the mediumallows the generated charges to be trapped in such positions, even whenthe electric field is removed off, thus yielding an electretcorresponding to the dosage, as shown in FIG. 35 (c).

Referring to the fourth and fifth electrostatic information recordingmedia wherein microparticles are photoconductive, the recording mediaare exposed on their overall surfaces to light after exposed toinformation-bearing light, as is the case with the first recordingmedium, whereby information-bearing charges can be stably retained inthe microparticles.

Referring to the sixth electrostatic information recording medium, it isexposed to information-bearing light while located in opposition to atransparent electrode 40, as illustrated in FIG. 36. When aphotoconductive layer 9 is to be laminated on the recording medium,however, information is first recorded in the electrostatic informationrecording medium. Then, a plastic film 80 coated with, e.g., an adhesiveagent 90 is applied on the photoconductive layer 9, as shown in FIG. 37.By releasing the plastic film 80, the photoconductive layer 9 is bondedto the plastic film adhesive layer to release a charge retaining layeras shown in FIG. 37 (c), thereby stabilizing information-bearingcharges. This is because the information-bearing charges tend to diffusethrough the photoconductive layer with the lapse of time.

Reference will now be made to a specific embodiment of the electrostaticinformation recording process wherein electrostatic information isrecorded as the positional information of fineparticles and played backas the electrostatic information. FIG. 38 is a view for illustrating anelectrostatic information recording step in which the fineparticles usedare photoconductive, and FIG. 39 shows an electrostatic informationrecording step in which electrically conductive microparticles are usedaccording to the present invention.

Referring to an electrostatic information recording medium 3, analuminium electrode of 1000 Å in thickness is vapor-deposited on asupport 15 of 1 mm thick glass, and is then provided thereon with aresinous layer 19 containing a 10 μm thick charge transporting material,below which a photoconductive particulate layer 12 having a particlesize of about 1 μm is spaced about 1 μm apart.

As illustrated in FIG. 38 (a), the electrostatic information recordingmedium 3 is arranged with respect to a photosensitive member 1 through agap of about 10 μm, and voltage is applied between electrodes 7 and 13to obtain polarity reverse to the transport polarity of the chargetransport material contained in the resinous layer 19. Upon light 18being incident from the photosensitive member 1, a portion of aphotoconductive layer 9, upon which the light strikes, is made soelectrically conductive that discharge takes place between it and theresinous layer 19, resulting in the accumulation of charges on thesurface of the resinous layer 19. Even when there are previously uniformbackground charges, further storage of charges occurs on the portion onwhich the light strikes. Subsequently, a power source 17 is put off, andthe electrostatic information recording medium 3 is released from thephotosensitive member 1 and exposed on its overall surface to light, asshown at 22. Thereupon, electron and positive hole carriers aregenerated in particles 12 in the portion exposed to light, and are inturn caused to migrate by a high electric field defined by surfacecharges, so that the opposite charges are neutralized and stably storedin the particles 12 as the information-bearing charges. Referring thento FIG. 38 (c), when the electrostatic information recording medium issubjected to resistance heating or the resinous layer 19 is heated andsoftened by other suitable means, the particles having theinformation-bearing charges migrate toward the electrode substrate, inwhich they remain confined by the curing of resin, so that theinformation-bearing charges in the particles are converted to positionalinformation.

The use of an electrically conductive material will now be explainedwith reference to FIG. 39.

Since the electrically conductive microparticles carry sufficientelectrons and positive holes, unlike the photoconductive microparticles,no uniform exposure is needed. Stored on the electrically conductiveparticles are charges corresponding to surface charges. After thecompletion of the exposure, the particles are allowed to migrate byheating the resinous layer in a similar manner as mentioned above.

It is noted that the photosensitive member 1 may come in contact withthe electrostatic information recording medium in contrast to the abovenon-contact arrangement. In this manner, the charges of the particulatelayer 12 are fixed in the resinous layer in the form of positionalinformation and stored over an extended period of time.

The present invention is characterized in that the positionalinformation in the particulate layer is reproduced as electrostaticinformation. In order to reproduce the information stored as theposition of the particles in the resinous layer in the case where themicroparticles used are photoconductive, voltage polarity is firstdetermined such that charges of the same polarity as that of the chargetransport material in the electrostatic information recording medium areformed by corona electrical charging at 26, thereby electrifying theoverall surface of the resinous layer in the recording medium, asillustrated in FIG. 40 (a). Then, the resinous layer is exposed on itsoverall surface to light shown at 22, as illustrated in FIG. 40 (b),whereby surface charges are accumulated on a region in which theinformation is stored, while carrier pairs of positive holes andelectrons are generated in a region in which no information is stored,one charges serving to negative surface charges and the other chargesmigrating through the resinous layer and re-joining to the oppositecharges of the electrode substrate, resulting in immediate erasion ofthe surface charges. Then, the surface charges of the region in whichthe information is stored are detected, as illustrated in FIG. 40 (c).Other means to form surface charges on the electrostatic informationrecording medium involves applying voltage to that recording mediumthrough, e.g., opposite electrodes instead of applying corona electricalcharging.

With the electrically conductive fineparticles, overall exposure may bedispensed with. The surface charges of the region in which noinformation is stored are erased by electrical conductivity, but thesurface charges of the region in which the information is stored in theform of positional information may be easily reproduced asinformation-bearing charges.

How to read the information-bearing charges recorded in theelectrostatic information recording medium will now be explained.

As an example, how to read potentials in the electrostatic informationrecording and playing-back processes according to the present inventionis illustrated in FIG. 41 wherein the same parts as in FIG. 1 areindicated by the same reference numerals. It is noted that referencenumeral 201 stands for a potential reader section, 203 a detectionelectrode, 205 a guard electrode, 207 a capacitor and 209 a voltmeter.

When the potential reader section 201 is located in opposition to thesurface of an electrostatic information recording medium 3 on whichcharges are built up, the detection electrode 203 is subjected to anelectric field defined by charges accumulated on a charge retaininglayer 11 of the recording medium 3, thus generating on its surfaceinduction charges in the amount equal to that of the charges on therecording medium 3. Since the capacitor 207 is charged with charges ofpolarity opposite to that of such induction charges in the same amount,there is a potential difference corresponding to the accumulated chargesbetween the capacitor's electrodes, which is in turn read on thevoltmete 209, thereby determining the potential of the charge retainer.Then, an electrostatic latent image can be produced in the form ofelectrical signals by scanning the surface of the electrostaticinformation recording medium with the potential reader section 201. Itis noted that only with the detection electrode 203, there is a drop ofresolving-power under the action of an electric field (an electric lineof force) defined over a range wider than the region of the recordingmedium opposite to the detection electrode; hence, the guard electrodemay be grounded around the detection electrode. According to such asystem, since the electric line of force acts vertically to a plane, itcan be obtained from only the region opposite to the detection electrode203. Thus, it is possible to read the potential of a region having anarea nearly equal to that of the detection electrode. Since the accuracyand resolving-power of potential reading vary largely depending upon thegeometry and size of the detection and guard electrodes as well as thespace between them and the electrostatic information recording medium,it is essentially required to design them while taking into account theoptimum conditions to meet the performance demanded.

FIG. 42 illustrates another system to read potentials, which is similarto that illustrated in FIG. 41, provided that the potential is detectedthrough an insulating protective film 211 on which the detection andguard electrodes are mounted.

According to this system designed to come in contact with theelectrostatic information recording medium for the detection ofpotentials, it is possible to keep constant the space between thedetection electrode and the recording medium.

FIG. 43 is a view showing still another system of how to readpotentials, wherein a needle-like electrode 213 is brought in directcontact with the electrostatic information recording medium to detectthe potential of the region of contact. In this system, it is possibleto obtain high resolving-power due to reductions in the area to bedetected. Higher reading rates are also achievable by the provision of aplurality of needle-like electrodes.

The above systems are all of the DC amplification type designed todetect DC signals in contact or non-contact relation. In what follows,the AC amplification type of systems will now be explained.

FIG. 44 is a view for illustrating a vibration electrode type ofpotential reading system, wherein 202 is a detection electrode, 204 anamplifier and 206 a meter.

The detection electrode 202 vibrates and is driven such that as timegoes by, it displaces with respect to a charged surface of anelectrostatic information recording medium 3. As a consequence, apotential across the detection electrode 202 varies with time at anamplitude corresponding to the electrostatic potential of the chargedsurface. This potential change-with-time is then obtained in the form ofa voltage change appearing across an impedance Z, and the AC componentis in turn amplified by the amplifier 204 through a capacitor C tomeasure the electrostatic potential of the charged surface in terms ofreadings on the meter 206.

FIG. 45 shows an example of a rotary detector, wherein a rotary blade isindicated at 208.

Between an electrode 202 and a charged surface of an electrostaticinformation recording medium 3, there is the electrically conductiverotary blade 208 driven for rotation by driving means (not illustrated).As a result, the detection electrode 202 is periodically andelectrically shielded relative to the electrostatic informationrecording medium 3. Potential signals varying periodically at anamplitude corresponding to the electrostatic potential of a chargedsurface is then detected by the detection electrode 202, and the ACcomponent is in turn amplified by an amplifier 204 for reading.

FIG. 46 illustrates an example of a vibrating-reed detector, whereinreference numerals 208 and 210 stand for a driving circuit and avibrating reed, respectively.

The vibrating reed 210 of one electrode forming a capacitor is vibratedby the driving circuit 208 to change the capacitor's capacity. As aresult, DC potential signals detected by the detector electrode 202 aremodulated, and the AC component is then amplified and detected. Withthis detector designed to convert a direct current to an alternatecurrent, it is possible to measure potentials with high sensitivity andsatisfactory stability.

FIG. 47 is a view showing a further example of potential reading, inwhich potentials are detected by computed tomography (CT) with anelongate detector electrode.

Where a detector electrode 215 is located across and in opposition to acharge-accumulated surface, the data obtained are in the form ofcurvilinear integration values along the detector electrode. In otherwords, data corresponding to the CT data are obtained. Thus, thedetector electrode is scanned on its overall surface as shown by anarrow in FIG. 47 (b) and at varied angles (θ) to gather the requireddata. The obtained data are then processed with CT algorithm, therebydetermining a potential distribution on a charge retainer.

It is noted that if a plurality of detector electrodes 215 are arrangedas shown in FIG. 48, then the data-gathering rates and hence the overallprocessing rates are improved.

FIG. 49 shows an example of a collector type detector, in whichreference numeral 212 denotes a grounded type metallic cylinder, 214 aninsulator and 216 a collector.

The collector 216 contains a radioactive substance which emits α rays.In the metallic cylinder, the air is thus ionized to form positive andnegative ion pairs. Under natural conditions, these ions tend todisappear by recombination and diffusion and are at equilibrium. In thepresence of an electric field, however, they collide repeatedly with airmolecules through thermal motion and migrate statistically toward theelectric field, thus carrying charges.

More specifically, for the reason that the air is made electricallyconductive by ions, an equivalent electrical resistance passage is takenas being defined between the collector 216 and a surrounding object.

Consequently, holds for stationary state the following equation:

    V.sub.2 =R.sub.2 V.sub.1 /(R.sub.1 +R.sub.2)

wherein R₀ is the resistance between the charged surface of theelectrostatic information recording medium 3 and the grounded metalliccylinder 212,

R₁ is the resistance between the charged body and the collector 216,

R₂ is the resistance between the collector 216 and the grounded metalliccylinder 212,

V₁ is the potential of the charged body, and

V₂ is the potential of the collector 216.

Thus, it is possible to find the potential of the electrostaticinformation recording medium by reading the potential of the collector216.

FIG. 50 is a view showing an example of an electron beam type ofpotential reader system, in which reference numeral 217 denotes anelectron gun, 218 electron beams, 219 a first diode and 220 a secondaryelectron amplifier section.

Electrons leaving the electron gun 217 are deflected by an electrostaticor electromagnetic deflector and scan a charged surface. A portion ofthe scanning electron beams joins to the charges of the charged surfaceinto a charging current, and so the potential of the charged surfacedrops to the equilibrium potential, correspondingly. Another portion ofthe beams is modulated and returned to the electron gun 217, and thencollides with the first diode 219. The resultant secondary electrons areamplified by the secondary electron amplifier 220 and obtained from theanode in the form of a signal output. As the return electron beams,reflected or secondary electrons may be used.

With the electron beam type of potential reader system, uniform chargesare formed on the medium after scanning, but a current corresponding toa latent image is detected during scanning. When the latent imagecarries negative charges, the accumulation of charges by electrons isreduced in a region (unexposed) carrying much charges, so that theresultant charging current is limited. However, a maximum chargingcurrent occurs, for instance, in a region where any charge is notpresent. On the contrary, positive charges define a negative type.

FIG. 51 illustrates another example of the potential reader system. Anelectrostatic information recording medium 3, on which an electrostaticlatent image is formed, is toner-developed. The colored surface is thenirradiated with light beams for scanning. The reflected light isconverted to electrical signals by a photoelectric converter 221. Withsuch a system, high resolving-power is attainable by reducing thediameter of light beams and the detection of electrostatic potentialscan be easily carried out in optical fashion.

FIG. 52 shows a further example of the potential reader system.Prismatic images R, G and B formed by such fine color filters as will bedescribed later are toner-developed. Then, the colored surface isirradiated with light beams to convert the reflected light to signals Y,M and C. In FIG. 52, reference numeral 223 denotes a scanning signalgenerator, 225 a laser, 227 a reflector, 229 a half mirror, 232 aphotoelectric converter and 233, 235 and 235 gate circuits.

With scanning signals from the generator 223, a colored surface isirradiated with laser beams from the laser 225 through the reflector 227and half mirror 229 for scanning. The light reflected from the coloredsurface is then fed into the photoelectric converter 231 to convert itto electrical signals. If the gate circuits 233, 235 and 237 arecontrolled for opening or closing synchronously with the signals fromthe generator 223, then they are controlled for opening or closingsynchronously with the pattern of the fine filters. Thus, it is possibleto obtain signals Y, M and C, even when they are not previously colored.

It is noted that even when a color image is split into three planes aswill be described later, signals Y, M and C are quite similarlyobtainable, again, without previously coloring them.

In the systems illustrated in FIGS. 51 and 52, it is required for thetoner-developed image to have the γ characteristic corresponding to thequantity of electrical charging of the latent image. For that reason, itis required to provide no threshold value with respect to an analogchange in the quantity of electrical charging. Given the correspondingrelationship, it is then possible to correct γ by electricalprocessings, even when the γ characteristic is in no coincidence withthe quantity of electrical charging.

FIG. 53 is a schematical view showing the process for reproducingelectrostatic images according to the present invention, in whichreference numeral 241 stands for a potential reader, 243 an amplifier,245 a CRT and 247 a printer.

Referring to this figure, a charge potential is detected by thepotential reader 241, and the resultant output is amplified by theamplifier 243 for display on the CRT 245 or printing-out with theprinter 247. In this case, the region to be read may be arbitarilyselected and output at any time, or may be repeatedly reproduced. Withthe electrostatic latent image obtained in the form of electricalsignals, it may then be recorded in other recording media, if required.

For the reproduction of surface charges with the printer 247, use may bemade of printing means such as thermal dye transfer, ink jet, hot-melttransfer, microcapsules, silver salts, toners or the like and displaymeans such as flat CRTs, plasma CRTs, liquid crystal displays,projection, LEDs, ELs, TV telephones, word processors, CGs, presentationor the like.

Reference will now be made to a protective film laminated on the chargeretaining layer in which information is recorded in this manner for thepurpose of improving the charge retainability of that layer.

In the electrostatic information recording media according to thepresent invention, it is preferred that as illustrated in FIG. 54 (a), aprotective layer 20 is laminated on the surface of the charge retaininglayer to prevent its failure or the attenuation of information-bearingcharges.

In order to form the protective film, use is made of one or a mixture ofmaterials showing such adhesion that it is releasable for reading duringthe reproduction of information such as reclaimed rubber,styrene-butadiene rubber, polyisoprene, butyl rubber, Buna-N(butadiene-acrylonitrile rubber), polyvinyl ethers (including ethyl orhigher hydrocarbon groups), polyacrylate esters (having ethyl or higherhydrocarbon groups), silicone rubber, polyterpene resins, gum rosins,rosin esters, rosin derivatives, oil-soluble phenolic resins,cumarone-indene resins and petrolic hydrocarbon resins. Such a materialor mixture is then formed into a film of hundreds Å to tens μm inthickness, which is in turn laminated on the surface of theelectrostatic information recording medium. Alternatively, an insulatingplastic film may be laminated on that surface with a releasable closecontact adhesive agent. As such adhesive agents, use may be made ofmaterials having a specific resistance of 10¹⁴ Ω·cm or higher such assilicone oil, dimethyl silicone oil, methylphenyl silicone oil, higherfatty acid-modified silicone oil, methyl chlorinated phenyl siliconeoil, alkyl-modified silicone oil, methyl hydrogen silicone oil, cyclicdimethyl polysiloxanes, silicone polyether copolymers, amino-modifiedsilicone oil, epoxy-modified silicone oil and insulating oil, which maybe used alone or in combination of two or more.

It may also be possible to laminate an insulating plastic film on thecharge retaining layer with the use of a bonding agent.

Furthermore, with the application of suitable means such as vapordeposition or spinner coating, a solution of an insulating plastic filmin a solvent may be applied on the charge retaining layer into a film ofhundreds Å to tens μm in thickness as measured upon drying.

The hot-melt transfer materials used may include EVA (ethylene-vinylacetate copolymers), EEA (ethylene-ethylene acrylate copolymers),polyamide resins, rosinous resins, hydrogenated petrolic resins,pinene-base resins, hydrocarbonic resins, synthetic rosinous resins,terpenic resins and wax which, if required, may be used in the form of amixture of two or more or with the addition of inorganic powders.Preference is given to a material allowing the protective layer to besubjected to hot-melt transfer at a temperature sufficient to preventthe attenuation-by-heating of charges on the charge retaining layer.

Information reading may be feasible from above the protective layer, andit is preferred to decrease the thickness of the protective film so asto improve the resolution of reading. This is because a sensor forreading should preferably have access to a region in which more chargesare stored for the purpose of improving the resolution of reading. Wherethe resolution of reading is negligible, it is possible to increase thethickness of the protective film.

If the protective film used is of such an adhesive type as mentionedabove, then it may be released from the charge retaining layer toreproduce the information on its surface.

As illustrated in FIG. 54 (b), a protecting film 20 may be laminated ona charge retaining layer 11 in a non-contact state. In this case, it ispreferable that a plastic film is used as the protective film andlaminated on that layer 11 through a spacer 28. A suitable space betweenthe charge retaining layer and the protective layer is in a range of 1to 50 μm, and a suitable spacer is formed of an organic material such asplastics. In order to reproduce the recorded information, the protectingfilm 20 may be released from the charge retaining layer 11 to read theinformation-bearing charges thereon. It is required that the spacer 28be releasably bonded to the charge retaining layer 11 with the aboveclose contact adhesive agents such as silicone oil.

FIG. 55 is a view showing an electrostatic information recording mediumin which audio and image information items are recorded according to thepresent invention.

Predetermined voltage is impressed between a photosensitive member 1 andan electrostatic information recording medium 3, and an electrostaticlatent image is recorded in that medium by subsequent exposure. In thepresent invention, image information carried by natural light, imageinformation carried by light of an illumination light source reflectedfrom a manuscript and the like are applied to the photosensitive member1 to record their latent images on the electrostatic informationrecording medium 3. At the same time, a laser light source or the likeis modulated by audio signals and audio information is applied to thephotosensitive member 1 in the form of optical information to record itin the electrostatic information recording medium 3. Thus, the imageinformation along with the audio information is recorded in theelectrostatic information recording medium 3.

FIGS. 56 and 57 are views showing zones for storing image and audioinformation items. Since the volume of audio information is much smallerthan that of image information, an image information storing zone P islocated at a central portion of the recording medium, while an audioinformation storing zone S is positioned at an end or edge portionthereof.

A process for recording image information along with audio informationin the electrostatic information recording medium according to thepresent invention is illustrated in FIG. 58, wherein reference numeral301 stands for a microphone, 302 an amplifier, 303 a laser, 304 anacoustic to optical converter, 305 a polygonal mirror and 306 a powersource.

The power source 306 is designed to apply predetermined voltage betweenthe photosensitive member 1 and the electrostatic information recordingmedium 3 by putting a switch 307 on or off. While the predeterminedvoltage is applied, the photosensitive member is then exposed to light300 carrying image information to form on the recording medium 3 alatent image potential corresponding to the image. Electrical signalsfed in through the microphone 301 and corresponding to a sound areamplified by the amplifier 302, and laser beams from the laser 303 aremodulated in response to audio signals by the acoustic to opticalconverter 304. The modulated signals are then applied to thephotosensitive member 1 by the scanning of the polygonal mirror 305 toform on the recording medium 3 a latent image potential corresponding tothe audio signals. Thus, the audio information is recorded along withthe image information in the electrostatic information recording medium3. As a result, when an image such as a landscape is recorded on theelectrostatic information recording medium 3, photographing conditions,etc. may be recorded in the form of sounds. It is thus possible toreproduce that image with appropriate comments.

In the foregoing embodiment, the light is modulated by a combination ofthe optical modulator with the polygonal mirror for scanning andexposure purposes. It is noted, however, that electron beam scanning maybe performed through a combination of CRTs with modulation means as isthe case with, e.g., a flying spot scanner (FSS for short) to conductscanning and exposure through the photosensitive member with lightemanating from blips on a cathode-ray tube. Alternatively, theelectrostatic information recording medium may be located in proximityand opposition to the tube plane of a sort of CRT including thereon agroup of needle electrodes for direct discharge recording in therecording medium through the needle electrodes upon which scanningelectron beams strike.

FIG. 59 is a view illustrating another recording process making use ofPCM modulation, wherein the same parts as illustrated in FIG. 58 areindicated by the same reference numerals. With the process of FIG. 59,it is possible to record high-quality audio information resistive tonoises, since audio signals are converted to digital signals by PCM 320.

FIG. 60 is a view showing a further recording process making use of acirculatory memory, in which reference numeral 321 denotes an A/Dconverter, 322 a circulatory memory and 323 a D/A converter.

In the instant embodiment, audio signals are subjected to A/D conversionfor recording in the circulating memory 322, and the output of thatmemory 322 is subjected to D/A conversion for recording. The circulatingmemory 322 has a storage capacity capable of storing audio informationover a constant period of time with its stored content beingsuccessively renewable, so that the audio information can be alwaysstored from a certain previous time up to the present time. Forinstance, if the storage capacity of the circulating memory is such thataudio information is recordable for one minute, then the audioinformation can be recorded from before 30 seconds of photographing toafter 30 seconds. It is thus possible to achieve a reproduction of thephotographed situation with real presence. For instance, if an image ofa steam locomotive can be photographed with sounds generated therefromand a shutter sound, then the reproduced image will remind a viewer ofthe situation where photographing was conducted.

Reference will now be made to the structure of card members in which theelectrostatic information recording medium of the present invention isused.

FIG. 61 (a) is a perspective view of a ROM type of electrostaticinformation recording card according to the present invention and FIG.61 (b) a sectional view taken along the line A--A of FIG. 61 (a) forshowing a protective film provided in place. FIG. 62 (a) is aperspective view of a DRAW type of electrostatic information recordingmedium and FIG. 62 (b) a sectional view taken along the line B--B ofFIG. 62 (a).

A card substrate 4 on which an electrostatic information recordingmedium 3 is to be placed may be formed of any material of any thickness,if its strength is sufficient to support the recording medium 3. Forinstance, use may be made of flexible plastic sheets such as vinylchloride sheets or rigid sheets such as glass sheets, ceramic sheets andmetal sheets (which may also serve as electrodes). Without recourse toan electrostatic information recording medium support 15, an electrode13 and a charge retaining layer may be laminated directly on the cardsubstrate 4 in that order. As the support, use may be made of a metalsheet which may also serve as an electrode.

The electrostatic information recording medium 3 may be embedded in orsticked to the card substrate 4 as shown in FIG. 61 or FIG. 62, after orbefore the reocrding of information.

Information recording cards 90 are broken down into a ROM type in whichinformation has already been recorded in the electrostatic informationrecording medium as shown in FIG. 61 and a DRAW type in whichinformation is not or partly recorded as shown in FIG. 62. For the DRAWtype, for instance, an adhesive plastic film, as already mentioned, mayreleasably be applied to the surface of an insulating layer as theprotective film. For recording, the protective film may be peeled off torecord information in an unrecorded region. After recording, theprotective film may be again applied to the surface of the insulatinglayer.

The recording mode of the electrostatic information recording mediaaccording to the present invention may be used as forgery-safe means forcards, etc. due to its unvisibleness. With the present recording media,planar information processing may be possible because of their increasedstorage capacity and plane recording being acheivable once by planarexposure. Input or output of electrical signals and planar input ofimage data are also possible. In addition, various data such as analog,digital, image, sound and (0·1) data are recordable. The present mediamay further be used as computer's external memories. The informationrecorded are easily erasable.

The electrostatic information recording media of the present inventionare not only usable as electrostatic recording cards but also applicableto magnetic cards and IC cards as well as ROM, DRAW and EDRAW types ofoptical cards and marking cards by changing information input meanswhile using the present media as masters. Further, they are usable invaried recording regions.

Therefore, the present media may be used as the recording media for,e.g., ID cards, prepaid cards, credit cards, electronic calculators,electronic pocketbooks, cameras, clinical charts, timetables, maps,charge locks (keys), miniature books, name cards, sensors, dustremovers, batteries, bar cords, Karaoke (playback and sound inputcombinations), communications means such as post cards, records, games,teaching aids and so on. The electrophotographic recording cardsaccording to the present invention may be used as the recording media inbanking systems, ID systems, prepaid systems, credit systems, ticketissuing systems, medical diagnosis systems, navigation systems, chargelock systems, communications systems, game systems, teaching systems andother systems.

The present invention will now be explained with reference to thefollowing examples.

EXAMPLE 1! Preparation of Electrostatic Information Recording Medium andits Charge Retainability

On a film of tetrafluoroethylene-hexafluoropropylene copolymer (FEP)(DuPont) having specific resistance of 10¹⁸ Ω·cm or more, waterabsorption of 0.01%, and film thickness of 12.5 μm, aluminum electrodewas laminated in thickness of 1000 Å by vacuum deposition (10⁻⁵ Torr),and electrostatic information recording medium was obtained.

On this electrostatic information recording medium, electric charge wasprovided by corona charging to have the surface potential of +100 V or-100 V, and the electric charge retaining property was measured.

When measured after leaving at room temperature and humidity for 30days, the surface potential was maintained at 95 V in both (+) and (-).(The same applies hereinafter.) In the acceleration test leaving at 60°C. and 20% R.H. for 30 days, the surface potential of 95 V wasmaintained. Under high humidity condition, leaving it at 40° C. and 95%R.H. for 30 days, the surface potential of 94 V was maintained.

EXAMPLE 2!

To a film of tetrafluoroethylene-perfluoroalkylvinylether copolymer(PFA) (DuPont) having specific resistance of 1×10¹⁸ Ω·cm or more, waterabsorption of 0.03%, and film thickness of about 12 μm, aluminumelectrode was laminated in thickness of 1000 Å by vacuum depositionmethod (10⁻⁵ Torr), and electrostatic information recording medium wasobtained.

On the electrostatic information recording medium thus obtained,electric charge was provided by corona charging to have the surfacepotential of +100 V or -100 V, and the electric charge retainingproperty was measured.

When measured at room temperature and humidity for 30 days, the surfacepotential was maintained at 93 V in both (+) and (-). (The same applieshereinafter.) In the acceleration test leaving at 60° C. and 20% R.H.for 30 days, the surface potential was maintained at 90 V. Under highhumidity condition, leaving at 40° C. and 95% R.H. for 30 days, thesurface electric charge of 90 V was maintained.

EXAMPLE 3!

On a glass substrate of 1 mm thick, aluminum electrode wasvacuum-deposited in thickness of 1000 Å by vacuum deposition method(10⁻⁵ Torr). Fluorine-containing resin CYTOP (trade name; Asahi GlassCo.; water absorption 0.01%, specific resistance 1×10¹⁸ Ω·cm) wasdissolved in perfluoro(2-butyltetrahydrofuran, and 5% solution of thiswas coated on the above aluminum electrode by blade coater. After dryingthis at 150° C., electrostatic information recording medium of 3 μmthick was prepared.

On the electrostatic information recording medium thus obtained,electric charge was provided by corona charging to have the surfacepotential of -100 V, and the electric charge retaining property wasmeasured.

When measured after leaving at room temperature and humidity for 30days, the surface potential was -90 V. In the acceleration test, leavingit at 60° C. and 20% R.H. for 30 days, the surface potential wasmaintained at -85 V. Under high humidity condition leaving at 40° C. and95% R.H. for 30 days, the surface electric charge of -90 V wasmaintained.

EXAMPLE 4!

To a film of about 25 μm thick (Nitto Denko) consisting ofpolytetrafluoroethylene (PTFE) having specific resistance of 1×10¹⁸ Ω·cmor more, water absorption of 0.01% or less, aluminum electrode waslaminated in thickness of 1000 Å by vacuum deposition method (10⁻⁵Torr), and the electrostatic information recording medium was obtained.

On the electrostatic information recording medium thus obtained,electric charge was provided by corona charging to have the surfacepotential of +100 V or -100 V, and the electric charge retainingproperty was measured.

When measured after leaving at room temperature and humidity for 30days, the surface potential was maintained at 93 V in both (+) and (-).(The same applies hereinafter.) In the acceleration test, leaving at 60°C. and 20% R.H. for 30 days, the surface potential was maintained at 90V. Under high humidity condition leaving at 40° C. and 95% R.H. for 30days, surface electric charge was maintained at 93%. Further, under hightemperature condition, leaving at 150° C. for 10 hours, the surfacepotential was maintained at 90 V.

EXAMPLE 5!

On a glass substrate of 1 mm thick, aluminum electrode was laminated inthickness of 1000 Å by vacuum deposition method (10⁻⁵ Torr). A copolymerwas prepared, which has repeating unit given by the above generalformula (1) (n=1) and intrinsic viscosity η! of 0.50 at 30° C. in asolvent, the main component of which is Florinat FC-75 (trade name; 3MCompany; perfluoro(2-butyltetrahydrofuran), and having glass transitiontemperature of 69° C., water absorption of 0.01% and specific resistanceof 1×10¹⁸ Ω·cm. This was dissolved in perfluoro(2-butyltetrahydrofuran)and 5% solution of this was coated on aluminum electrode by spin coatingat 1500 rpm for 20 sec. After drying, the electrostatic informationrecording medium of about 3 μm thick was prepared.

On the electrostatic information recording medium thus obtained,electric charge was provided to have the surface potential of -100 V bycorona charging, and the electric charge retaining property wasmeasured.

When measured after leaving at room temperature and humidity for 30days, the surface potential was -93 V. In the acceleration test, leavingat 60° C. and 20% R.H. foe 30 days, the surface potential of -78 V wasmaintained. Under high humidity condition, leaving at 40° C. and 95%R.H. for 30 days, the surface electric charge of -90 V was maintained.

EXAMPLE 6!

On a glass substrate of 1 mm thick, aluminum electrode was laminated inthickness of 1000 Å by vacuum deposition method (10⁻⁵ Torr). A copolymerwas prepared, which has repeating unit given by the above generalformula (1) (n=2) and (2) (n=2) and instrinsic viscosity of 0.55 at 30°C. in a solvent, main component of which is Florinat FC-75 (trade name;3M Company; perfluoro(2-butyltetrahydrofuran), and having glasstransition temperature of 108° C., water absorption of 0.01%, andspecific resistance of 1×10¹⁸ Ω·cm. This was dissolved inperfluoro(2-butyltetrahydrofuran), and 7% solution of this was coated onthe above aluminum electrode at 1500 rpm for 20 sec. by spin coater.After drying, electrostatic information recording medium of about 3 μmthick was prepared.

On the electrostatic information recording medium thus obtained,electric charge was provided to have the surface potential of -100 V bycorona charging, and the electric charge retaining property wasmeasured.

When measured after leaving at room temperature and humidity for 30days, the surface potential was -90 V. In the acceleration test, leavingat 60° C. and 20% R.H. for 30 days, surface potential of -85 V wasmaintained. Under high humidity condition leaving at 40° C. and 95% R.H.for 30 days, the surface electric charge of -90 V was maintained.

EXAMPLE 7!

On a glass substrate of 1 mm thick, aluminum electrode was laminated inthickness of 1000 Å by vacuum deposition method (10⁻⁵ Torr). A copolymerwas prepared, which has repeating unit given by the above generalformula (1) (blended substance of n=1 and n=2) and general formula (2)(n=2) and has intrinsic viscosity η! of 0.44 at 30° C. in a solvent,main component of which is Florinat FC-75 (trande name; 3M Company;perfluoro(2-butyltetrahydrofuran), and having glass transition point of91° C., water absorption of 0.01%, and specific resistance of 1×10¹⁸Ω·cm. This was dissolved in perfluoro(2-butyltetrahydrofuran), and 5%solution of this was coated on the above aluminum electrode by spincoater. After drying, electrostatic information recording medium ofabout 3 μm thick was prepared.

On the electrostatic information recording medium thus obtained,electric charge was provided to have the surface potential of -100 V bycorona charging, and the electric charge retaining property wasmeasured.

When measured after leaving at room temperature and humidity for 30days, the surface potential was -90 V. In the acceleration test, leavingat 60° C. and 20% R.H. for 30 days, the surface potential of -80 V wasmaintained. Under high humidity condition, leaving at 40° C. and 95%R.H. for 30 days, the surface electric charge of -90 V was maintained.

EXAMPLE 8!

On a glass substrate of 1 mm thick, aluminum electrode was laminated inthickness of 1000 Å by vacuum deposition method (10⁻⁵ Torr). A copolymerwas prepared, which has repeating unit given by the above generalformula (1) (n=1) and --(CF₂ --CF₂)-- and in which cyclic structuralunit derived from perfluoroallylvinylether accounts for 81 wt %, andwhich has intrinsic viscosity η! of 0.425 at 30° C. in a solvent, themain component of which is Florinat FC-75 (trade name; 3M Company;perfluoro(2-butyltetrahydrofuran), and having water absorption of 0.01%and specific resistance of 1×10¹⁸ Ω·cm. This was dissolved inperfluoro(2-butyltetrahydrofuran), and 5% solution was coated on theabove aluminum electrode by spin coater. After drying, electrostaticinformation recording medium of about 3 μm thick was prepared.

On the electrostatic information recording medium thus obtained,electric charge was provided by corona charging to have the surfacepotential of -100 V, and the electric charge retaining property wasmeasured.

When measured after leaving at room temperature and humidity for 30days, the surface potential was -93 V. In the acceleration test, leavingat 60° C. and 20% R.H. for 30 days, the surface potential of -70 V wasmaintained. Under high humidity condition leaving at 40° C. and 95% R.H.for 30 days, the surface electric charge of -90 V was maintained.

EXAMPLE 9!

On a glass substrate of 1 mm thick, aluminum electrode was laminated inthickness of 1000 Å by vacuum deposition method (10⁻⁵ Torr). A copolymerwas prepared, which consists of repeating unit given by the abovegeneral formula (1) (n=1) and: ##STR17## and in which cyclic structuralunit derived from perfluoroallylvinylether occupies 89 wt %, and whichhas intrinsic viscosity η! of 0.35 at 30° C. in a solvent, maincomponent of which is Florinat FC-75 (trade name; 3M Company;perfluoro(2-butyltetrahydrofuran), and having glass transitiontemperature of 61° C., water absorption of 0.01%, and specificresistance of 1×10¹⁸ Ω·cm. This was dissolved inperfluoro(2-butyltetrahydrofuran), and 5% solution was coated on theabove aluminum electrode by spin coater. After drying, electrostaticinformation recording medium of about 3 μm thick was prepared.

On the electrostatic information recording medium thus obtained,electric charge was provided to have the surface potential of -100 V bycorona charging, and the electric charge retaining property wasmeasured.

When measured after leaving at room temperature and humidity for 30days, the surface potential was -90 V. In the acceleration test, leavingat 60° C. and 20% R.H. for 30 days, the surface potential of -60 V wasmaintained. Under high humidity condition leaving at 40° C. and 95% R.H.for 30 days, the surface electric charge of -90 V was maintained.

EXAMPLE 10!

An aluminium electrode was formed to a thickness of 1000 Å on a glasssubstrate of 1 mm in thickness by vacuum vapor deposition (10⁻⁵ Torr).With the use of a blade coater, the electrode was then overcoated with asolution of a polyester resin having a glass transition temperature of67° C. and a specific resistance of 7×10¹⁷ Ω·cm (available under thetrade name of Vylon 200 from Toyobo) dissolved in a mixed solvent of37.5 parts by weight of methyl ethyl ketone and 37.5 parts by weight oftoluene, followed by drying, thereby obtaining an electrostaticinformation recording medium having a polyester film thickness of about10 μm.

The thus obtained recording medium was charged thereon at +100 V or -100V of surface potential by the control of corona charging and theelectric charge retaining property was measured.

After allowed to stand at room temperature and humidity for 30 days, thesurface potential was found to be 80 V, both +and -. When the recordingmedium was left to an environment of 80° C. and 20% R.H. in anaccelerated test, the surface potential reduced to 0 V, both +and -,within one day. In a similar manner as mentioned above, some ofelectrostatic information recording media were formed as chargeretaining layers by using polyester resins having varied glasstransition temperatures (available under the trade names of Vylon 500,GK150 and GK103 from Toyobo with glass transition temperatures of 4° C.,26° C. and 47° C., respectively). After allowed to stand at 40° C. forone hour, the relation between the glass transition temperatures and thesurface potentials was found. The results are plotted in FIG. 65,wherein A shows the charge retaining ratio for each glass transitiontemperature.

EXAMPLE 11!

An aluminium electrode was formed to a thickness of 1000 Å on a glasssubstrate of 1 mm in thickness by vacuum vapor deposition (10⁻⁵ Torr).The Al electrode was then vapor-deposited at several Torr withpoly-p-xylylene (available under the trade name of Parylene from TomoeKogyo/Union Carbide and having a glass transition temperature of 80° to100° C., a specific resistance of 9×10¹⁶ Ω·cm and a water absorption of0.01%), thereby obtaining an electrostatic information recording mediumhaving a film thickness of about 10 μm.

The thus obtained recording medium was charged thereon at +100 V or -100V of surface potential by the control of corona charging and its chargeretaining property was measured.

After allowed to stand at room temperature and humidity for 30 days, thesurface potential was found to be 80 V. Under accelerated testingconditions expressed in terms of 60° C., 20% R.H. and 30 days, a surfacepotential of 60 V was obtained. Even after allowed to stand at 40° C.under high-humidity conditions of 95% R.H. for 30 days, the surfacepotential were maintained at 60 V. This indicates that the obtainedelectrostatic information recording medium is a superior recordingmedium.

EXAMPLE 12!

After an aluminium electrode was formed to a film thickness of 1000 Å ona polyester resin (PET) film (having a thickness of 12 μm, availableunder the trade name of Lumirror S available from Toray, and having aglass transition temperature of 69° C., a water absorption of 0.4% and aspecific resistance of 1×10¹⁸ Ω·cm) by vacuum vapor deposition (10⁻⁵Torr). A film was laminated on a glass substrate of 1 mm in thicknessfaced to the electrode with a double-side adhesive tape to make anelectrostatic information recording medium.

The thus obtained recording medium was charged thereon at +100 V or -100V of surface potential by the control of corona charging and its chargeretaining property was measured.

After allowed to stand at room temperature and humidity for 30 days, thesurface potential was 50 V, both +and -.

EXAMPLE 13!

An aluminium electrode was formed to a film thickness of 1000 Å on apolyethylene naphthalate (PEN) film (having a thickness of 12 μm,available under the trade name of Q Film from Teijin, and having a glasstransition temperature of 113° C. and a water absorption of 0.4%) byvacuum vapor deposition (10⁻⁵ Torr) to make an electrostatic informationrecording medium.

The thus obtained recording medium was charged thereon at +100 V or -100V of surface potential by the control of corona charging and its chargeretaining property was measured.

After allowed to stand at room temperatuer and humidity for 30 days, thesurface potential was found to be 80 V, both +and -, by measurement.Under accelerated testing conditions expressed in terms of 60° C. and20% R.H. for 30 days, the surface potential was found to be 80 V bymeasurement.

COMPARISON EXAMPLE!

An aluminium electrode was formed to a thickness of 1000 Å on a glasssubstrate of 1 mm in thickness by vacuum vapor deposition (10⁻⁵ Torr).With the use of a blade coater, the Al electrode was then overcoatedwith a solution of styrene-butadiene rubber (available under the tradename of Kaliflex TR4113 from Shell) having a glass transitiontemperature of -70° C., a water absorption of 0.3% and a specificresistance of 1×10¹⁵ Ω·cm dissolved in a mixed solvent of 37.5 parts byweight of methyl ethyl ketone and 37.5 parts by weight of toluene,followed by drying, whereby an electrostatic information recordingmedium having a film thickness of about 10 μm was obtained.

The thus obtained recording medium was charged thereon at +100 V or -100V of surface potential by the control of corona charging and its chargeretaining property was measured.

After allowed to stand at room temperature and humidity for 30 days, thesurface potential was found to be 0 V by measurement. Upon exposed to anenvironment of 60° C. and 20% R.H., the surface potential was also foundto be 0 V after the lapse of one day.

EXAMPLE 14!

Under sufficient agitation, 1% by weight (0.2 g) of a curing agent (ametal catalyst available under the trade name of CR-15) was added to amixed solution composed of 10 g of a methylphenyl silicone resin in an1:1 solvent of xylene and butanol. With the use of a doctor blade 4mill, the resulting solution was coated on a glass substratevapor-deposited with Al at a thickness of 1000 Å. Subsequent 1-hourdrying at 150° C. gave an electrostatic information recording medium (a)having a film thickness of 10 μm.

In a similar manner as mentioned above, the above mixed solution wascoated on a 100 m polyester film vapor-deposited with Al at a thicknessof 1000 Å, followed by drying, to obtain a film-like electrostaticinformation recording medium (b).

The above mixed solution was also coated on a 4-inch disc-like acrylsubstrate (having a thickness of 1 mm) vapor-deposited with Al at athickness of 1000 Å by means of a spinner at 2000 rpm. Subsequent 3-hourdrying at 50° C. gave a disc-like electrostatic information recordingmedium (c) having a film thickness of 7 μm.

Similar coating with the above mixed solution containing additionally0.1 g of zinc stearate and drying gave an electrostatic informationrecording medium (d) having a film thickness of 10 μm.

On a glass substrate (thickness: about 500 A, 100 Ω/□) provided withITO, the above mixture solution was coated by the same procedure and wasdried. Thus, electrostatic information recording medium havingtransparent support member, electrode and electric charge retaininglayer was obtained.

On a PET film of 125 μm (Mitsubishi Kasei; 300-400 Ω/□) provided withITO, the above mixture solution was coated by the same procedure and wasthen dried. Thus, electrostatic information recording medium havingtransparent and flexible support member, electrode and electric chargeretaining layer was obtained.

EXAMPLE 15!

10 g of 2,2- 4-(4-aminophenoxy)phenyl!propane was dissolved in 100 g ofN-methylpyrolidone. Adding 10 g of pyromelitic acid dianhydride to itgradually, this was agitated at room temperature for 5 hours.

Then, this solution was coated on the surface of transparent ITOelectrode layer (thickness: 550 Å, 80 Ω/□ on glass substrate, which hadbeen moistened ill advance by N-methylpyrolidone solvent by bladecoater. After drying this at 150° C. for one hour, it was heated at 250°C., and the electrostatic information recording medium of about 10 μmthick was obtained.

On the surface of the electrostatic information recording medium thusobtained, electric charge was provided to have the surface potential of+100 V or -100 V, and the electric charge retaining property wasmeasured.

When measured after leaving it at 60° C. and 20% R.H. for 10 days,surface potential of 70 V was maintained. When it was left on a heatingplate kept at 150° C. for 6 hours, surface potential of 78 V wasmaintained.

Preparation of photosensitive member

EXAMPLE 16! Single-Layer Photosensitive Member

A mixed solution composed of 10 g of poly-N-vinylcarbazole (availablefrom Anan Koryo), 10 g of 2,4,7-trinitrofluorenone, 2 g of a polyesterresin (a binder available under the trade name of Vylon 200 from Toyobo)and 90 g of tetrahydrofuran (THF) was prepared in a dark place and itwas then spread on a glass substrate (of 1 mm in thickness) sputteredwith In₂ -O₃ SnO₂ at a thickness of about 1000 Å with the use of adoctor blade. The product was dried at 60° C. for about 1 hour whilesupplying air thereto to obtain a photosensitive layer having aphotoconductive layer of about 10 μm in thickness. For complete dryingpurposes, air drying was carried for further one day.

EXAMPLE 17! a-silicon Photosensitive Member

Production of an amorphous silicon aSi:H inorganic photosensitive member

(1) Cleaning of substrate

A 23 mm long, 16 mm wide and 0.9 mm thick, optically polished glasssubstrate, sold by Corning under product designation 7059 glass, andhaving a thin transparent SnO₂ electrode layer formed on its one face,was subjected to ultrasonic cleaning in each of trichloroethane, acetoneand ethanol in the described order. The glass was cleaned in eachcleaning liquid for 10 minutes.

(2) Preparation of equipment

A reaction receptacle and gas pipes were placed within a reactionchamber 404, which was evacuated by a diffusion pump to 10⁻⁵ Torr forcarrying out heating at 150°-350° C. for one hour, and after heating thechamber was cooled.

(3) Deposition of aSi:H(n⁺)

The substrate cleaned was set on the anode 406 in the reaction chamber404 in FIG. 64 with good thermal conduction, and the reaction chamberwas evacuated to 10⁻⁵ Torr by the diffusion pump, in which condition theheater 408 was adjusted so that the glass substrate was increased to250° C. At this temperature condition, a gas of B₂ H₆ /SiH₄ (1000 ppm)was allowed to flow into the reaction chamber 404 by controlling theneedle valve and the rotation of the PMB so that pressure in the chamberwas 200 m Torr. After the inner pressure of the reaction chamber becameconstant, 40 W of Rf power 402 (13.56 MHz) was put to work through theMatching box 403 to form plasma between the cathode and the anode. Thedeposition was performed for 4 minutes, then Rf power was disconnected,and the needle valve was closed. This resulted in about 0.2 μm thickaSi:H(n⁺) which constituted a blocking layer was deposited on thesubstrate.

(4) Deposition of aSi:H

A silane gas of 100% (SiH₄) was entered into the reaction chamber in thesame manner as in (3) Deposition of aSi:H. When the inner pressure inthe chamber became constant, 40 W Rf power 402 (13.56 MHz) was similarlyconnected through the matching box 403 to form a plasma which wasmaintained for 70 minutes. After the deposition was completed, the Rfpower was disconnected and the needle valve was closed. After thesubstrate was cooled by turning off the heater 408, it was taken out. Asa result, about 18.8 μm thick film was deposited on the aSi:H(n⁺) film.Thus, a photosensitive member including SnO₂ /aSi:H(n+) blockinglayer/aSi:H(non doped) 20 μm was produced.

EXAMPLE 18!

Fabrication of amorphous selenium-tellurium inorganic photosensitivemember

A mixture of metallic particles obtained by mixing selenium (Se) withtellurium (Te) in a proportion of 13% by weight was used. A Se-Te thinfilm was formed on an ITO glass substrate by vapor depositing themetallic mixture at a vacuum degree of 10⁻⁵ Torr under resistanceheating. The film has a thickness 1 μm. Subsequently at the same vacuumlevel, Se vapor deposition was similarly carried out under resistanceheating to form a 10 μm a-Se layer on the a-Se-Te layer.

EXAMPLE 19!

Production of function separated photosensitive member (forming ofcharge generation layer)

A liquid mixture consisting of 0.4 g of chlorodianeblue and 40 g ofdichloroethane was placed in a stainless receptacle having a volume 250ml, and then 180 ml of glass beads No. 3 was added. These material waspulverized by a vibrating mill (sold by Yasukawa Denki Seisakusho underproduct designation ED9-4) for about 4 hours to produce chlorodianebluewith particle size 5 μm or smaller, to which after the glass beads beingfiltered, 0.4 g of polycarbonate, sold by Mitsubishi Gas Kagaku undertrade name Upiron E-2000 was stirred for about 4 hours to form asolution, which was coated by using a doctor blade on the 1 mm thickglass substrate, having about 1000 Å thick In₂ 0₃ -SnO₂ film sputteredon it, to form an about 1 μm thick charge generation layer which wasdried at room temperature for one day.

Formation of a charge transport layer

A liquid mixture, containing 0.1 g of4-dibenzylamino-2-methylbenzaldehyde-1,1'-diphenylhydrazone, 0.1 g ofpolycarbonate (Upiron E-2000), and 2.0 g of dichloroethane, was coatedby a doctor blade over the charge generation layer, above mentioned, toform an about 10 μm thick charge transport layer, which was dried at 60°C. for 2 hours.

EXAMPLE 20!

Formation of a charge generation layer

10 g of butyl acetate, 0.25 g of butylal resin, (sold by Sekisui Kagaku,Japan under trade name SLEC), 0.5 g of a ClO₄ salt of azulenium havingthe following equation: ##STR18## and 33 g of glass beads No. 1 weremixed and stirred by a touch mixer for one day to prepare sufficientlydispersed material, which was coated by using a doctor blade orapplicator on ITO deposited on a glass plate and then dried at 60° C.for more than 2 hours to form a dried film having a thickness 1 μm orless.

Formation of a charge transport layer

9.5 g of tetrahydrofuran, 0.5 g of polycarbonate, sold by Mitsubishi GasKagaku, Japan, under trade name of Upiron E-2000, 0.5 g of a hydrazonederivative (sold by Anan Koryo, Japan, under product designation CTC191)having the following equation: ##STR19## were mixed and then coated byusing a doctor blade over the charge generation layer above described toform a coating, which was dried at 60° C. for 2 hours with a filmthickness 10 μm or less.

EXAMPLE 21!

Formation of an electron generation layer

20 g of tetrahydrofuran, 0.5 g of a butylal resin, sold by SekisuiKagaku, Japan, under trade name of SLEC, 0.25 g oftitanylphthalocyanine, 0.25 g of 4,10-dibromoanthanthrone, and 33 g ofglass beads No. 1 were stirred by a touch mixer for one day to obtain asufficiently dispersed material, which was coated by using a doctorblade or applicator over ITO laminated over a glass plate and then driedat 60° C. for 2 or more hours to produce a dried coating with athickness 1 μm or less.

Fabrication of a charge transport layer

0.5 g of polycarbonate (produced by Mitsubishi Gas Kagaku, Japan, underthe trade name of Upiron E-2000), and 0.5 g of the above-describedhydrazone derivative (sold by Anan Koryo, Japan, under productdesignation CTC191) were dissolved into 9.5 g of dichloroethane toprepare a coating material, which was coated by using a doctor bladeover the charge generation layer, above described, and then dried for 2hours at 60° C. for 2 hours or more to form a film having a thickness 10μm or larger.

EXAMPLE 22!

Forming of a barrier layer of charge injection layer

A soluble polyamide (sold by Toa Gosei Kagaku, Japan, under productdesignation FS-175SV10) was coated by a spin coater with a thickness0.5-1 μm on ITO laminated on a glass plate and then dried at 60° C. for2 hours or more.

Forming of a charge generation layer 10 g of butyl acetate, 0.25 g of abutylal resin (sold by Sekisui Kagaku, Japan, under the trande nameSLEC), 0.5 g of the above-described ClO₄ salt of azulenium and 33 g ofglass beads No. 1 were mixed and stirred by a touch mixer for one day toproduce a sufficiently dispersed material, which was coated by using adoctor blade or an applicator over the barrier layer of charge injectionabove mentioned and then dried at 60° C. for 2 hours or more to form adried coating having a thickness 1 μm or less.

Formation of a charge transport layer 0.5 g of polycarbonate (sold byMitsubishi Gas Kagaku, Janan, under trade name Upiron E-2000) and 0.5 gof the above-described hydrazone derivative (sold by Anan Koryo underproduct designation CTC191 were dissolved into 9.5 g of tetrahydrofuranto prepare a coating material, which was coated by using a doctor bladeon the charge generation layer and then dried at 60° C. for 2 hours ormore to form a coating with a thickness 10 μm or less.

EXAMPLE 23!

Formation of a barrier layer of charge injection layer

A soluble polyamide (sold by Toa Gosei Kagaku under product designationFS-175SV10) was applied with a thickness 0.5-1 μm over ITO, laminated ona glass plate, and then dried at 60° C. for 2 hours or more.

Formation of a charge generation layer

20 g of tetrahydrofuran, 0.5 g of a butylal resin (sold by SekisuiKagaku under the trande name SLEC), 0.25 g of titanylphalocyanine, 0.25g of 4,10-dibromoansuansuron and 33 g of glass beads No. 1 were stirredby a touch mixer for one day to form a sufficiently dispersed material,which was applied by a doctor blade or an applicator on theabove-mentioned barrier layer of change injection and was then dried at60° C. for 2 hours or more to form a dried coating having a thickness 1μm or less.

Formation of a charge transport layer

0.5 g of polycarbonate (sold by Mitsubishi Gas Kagaku under the trandename Upiron E-2000) and 0.5 g of the above-mentioned hydrazonederivative (sold by Anan Koryo under product designation CTC191) weredissolved into 9.5 g of dichloroethane as a solvent to prepare a coatingmaterial, which was coated by using a doctor blade over theabove-mentioned charge generating layer and then dried at 60° C. for 2hours to form a dried coating having a thickness 10 μm or larger.

EXAMPLE 24!

Formation of an electrode layer for a photosensitive member

An indium tin oxide (ITO) having specific resistance 100 Ω·cm² wascoated by sputtered over a blue glass plate in condition of 100° C. bythe substrate temperature and 10⁻³ Torr under oxy-atmosphere. Thismaterial may be deposited by EB method.

Formation of a barrier layer of charge injection

Silicon dioxide was sputtered over the above-described electrode layer.The thickness of the silicon dioxide may be 100-3000 Å and aluminumoxide may be used in place of silicon dioxide. EB method may be adoptedinstead of sputtering for deposing the layer.

Formation of charge generation layer

A selenium-tellurium layer containing 13% by weight of tellurium wasdeposited on the above barrier layer of charge injection by resistanceheating with a thickness 2 μm or less.

Formation of a charge transport layer

A selenium layer was deposited on the above-mentioned charge generationlayer by resistance heating with a thickness 10 μm or less.

EXAMPLE 25!

The photosensitive member given by FIG. 9 (c) was prepared as follows:

On one side of a glass substrate, acqueous solution of modified alkylsilicate (ETSB-5000; TSB Development Center, Inc.) was formed by screenprinting method. After drying and curing at 150° C., recessed portionwas furnished.

Then, the electrode layer of ITO electrode (thickness: 500 Å; surfaceresistance 100 Ω/□) was formed by sputtering.

On this substrate, photoconductive layer of PVK was formed by the sameprocedure as in the Example 16.

EXAMPLE 26!

The photosensitive member as given in FIG. 9 (d) was prepared asfollows:

Electrically conductive paste (3301C; Three Boud Co.) was prepared onITO electrode (thickness 500 Å; surface resistance 100 Ω/□) by screenprinting method. After drying and curing at 150° C., electricallyconductive recessed portion was furnished.

The photoconductive layer of PVK was formed by the same procedure as inthe Example 16 on this substrate.

EXAMPLE 27!

The photosensitive member as given in FIG. 9 (e) was prepared asfollows:

On one side of a glass substrate, ITO electrode (thickness 500 Å;surface resistance 100 Ω/□) was formed, and a stainless steel plate chipwas placed on it. On this substrate, a-Se photoconductive layer wasformed by the same procedure as in the Example 18 was formed. a-Se layerwas 2 μm thick.

Next, the chip was removed, and the lacking portion of thephotoconductive layer was formed.

EXAMPLE 28!

The photosensitive member as given in FIG. 9 (f) was prepared asfollows:

On one side of a glass substrate, a mask was closely fit, prepared froma partially perforated stainless steel plate. Then, light screeningportion was formed by vacuum-depositing aluminum of about 1000 Å thickby vacuum depositoin method.

Next, on the side opposite to the vacuum-deposited side, ITO electrode(thickness 500 Å; surface resistance 100 Ω/□) was furnished bysputtering.

On this substrate of ITO electrode side, photoconductive layer wasformed by the same procedure as in the Examples 16-21.

EXAMPLE 29!

The photosensitive member as given in FIG. 9 (g) was prepared asfollows:

On one side of a glass substrate, ITO electrode (thickness 500 Å;surface resistance 100 Ω/□) was furnished. Then, a mask, prepared from apartially perforated stainless steel plate, was closely fit to theelectrode layer, and plasma processing was performed in H₂ atmosphere.Thus, ITO was reduced to a metal plate, and light screening portion wasformed.

Next, photoconductive layer was formed by the same procedure as in theExamples 16-21.

EXAMPLE 30!

The photosensitive member of FIG. 9 (h) was prepared as follows:

On one side of a glass substrate, a mask was closely fit, prepared froma partially perforated stainless steel plate. Then, aluminum of about1000 Å thick was vacuum-deposited by vacuum deposition method to formlight screening portion.

Next, on the same side as the vacuum-deposited side, the same ITOelectrode as the above was formed.

On this substrate, photoconductive layer was formed by the sameprocedure as in the examplies 16-21.

EXAMPLE 31!

The photosensitive member of FIG. 9 (i) was prepared as follows:

On one side of a glass substrate, ITO electrode (thickness 500 Å;surface resistance 100 Ω/□) was formed. Stainless steel plate chip wasplaced on it, and a-Se photoconductive layer was formed on thissubstrate by the same procedure as in the Example 18. Then, the chip wasremoved, and the lacking portion of the photoconductive layer wasformed.

EXAMPLE 32!

Aqueous solution of gelatin (solid components: 20%) was prepared byadding ammonium dichromate to gelatin by 10 wt %. This was heated at 40°C. and was coated on a glass substrate by spin coating method at 2000rpm for 30 sec. Then, this was dried in an oven kept at 90° C. for onehour, and a gelatin photosensitive layer of 1 μm thick was obtained.

Next, chromium mask plate with striped pattern was placed on gelatinsurface with mask surface and gelatin surface facing to each other.Ultraviolet ray contact exposure (mercury lamp) was performed from theside of chromium mask plate. After the exposure of 20 sec., the mediumwas taken out and was immersed in the aqueous solution at 40° C. Thenon-exposed portion was dissolved, and negative pattern was formed.After drying in an over for one hour, patterning was completed.

Next, the medium thus patterned was immersed in R-dye solution (Kayanolmilling red RS; Nippon Kayaku); 5 g/liter, heated at 50° C. for 3minutes and was taken out. After drying by water-washing drying at 2000rpm for 10 sec., the patterned gelatin layer was dyed in red color.Further, acryl resin solution (JSS; Nippon Synthetic Rubber Co.) wascoated as protective layer by spinner at 2000 rpm for 10 sec., and thefilm of 0.3 μm thick was obtained after curing at 150° C. for 30minutes.

This process was repeated on G, and B by the same procedure, deviatingthe position of the patterned chromium mask plate. Finally, dyeing typestriped color filter having R, G and B aligned at the line width of 10μm was prepared. (G: Kayanol milling green 5 GW; B: Kayanol cyanine 6B;5 g/liter aqueous solution was used in both cases.)

Next, acryl resin solution (JSS; Nippon Synthetic Rubber Co.) was coatedas protective layer by the same procedure as above. after this was driedand cured to form a film of 0.3 μm, ITO electrode (thickness 500 Å;surface resistance 100 Ω/□) was formed.

On this substrate, photoconductive layer was formed by the sameprocedure as in the Examples 16-21.

EXAMPLE 33!

A glass plate of 1 mm thick (Corning Glass; 7059 glass; square of 50mm×50 mm) was polished on both sides (flatness: 0.1 μm). Aqueoussolution of gelatin (solid components: 20%) was prepared by addingammonium dichromate to gelatin by 10 wt %. This was heated at 40° C. andwas coated on the above substrate by spin coating method at 2000 rpm for30 sec. After drying in an oven kept at 90° C. for one hour, a mediumhaving gelatin photosensitive layer of 1 μm thick was obtained.

Next, chromium mask plate (100 mm×100 mm square) having rectangularportion of 18 mm×13 mm to be exposed was placed on the above gelatinlayer with the mask surface facing to the gelatin surface. Ultravioletray contact exposure (mercury lamp) was performed from the side ofchromium mask plate. After the exposure of 20 sec., the medium was takenout and was immersed in water solution kept at 40° C. The nonexposedportion was dissolved, and negative pattern was formed. After drying itin an oven for one hour, the patterning was completed.

After the patterning was completed, the medium was immersed for 3minutes in aqueous solution (5 g/liter) of R-dye solution (Kayanolmilling red RS; Nippon Kayaku) heated at 50° C. After taking it out, itwas dried by water-washing spin drying (2000 rpm; 10 sec.), and thepatterned gelatin layer was dyed in red. Further, acryl resin solution(JSS; Nippon Synthetic Rubber Co.) was coated by spinner coating (2000rpm; 10 sec.) and was cured (150° C.; 30 minutes).

Thus, a protective layer of 0.3 μm was formed, and color filter coloredin red (R) was obtained.

By the same process as above, two patterened media were prepared.Instead of R-dye solution in the above dyeing process, the patternedmedia were dyed in the same condition in aqueous solution (5 g/liter) ofG-dye solution (Kayaminol milling green 5GW) and B dyeing solution(Kayaminol cyanine 6B). The protective layer was formed by the sameprocedure, and color filters colored in green (G) and blue (B) wereobtained.

The color filters of R, G and B thus obtained were cut by a glass cutterto leave only the dyed portions (18 mm×13 mm), and color separationfilters of the same size for 3 colors were prepared.

Each of these color separation filters of R, G and B was disposed on thefront of Ir, Ig and Ib of 3-plane division optical system as shown inFIG. 12 (b). The size of each of these Ir, Ig and Ib surfaces is thesame as the size of color separation filter: 18 mm×13 mm. Next, a-Sephotosensitive member prepared in the Example 18 was disposed with glasssurface placed face-to-face to each surface of R, G and B colorseparation filters so that each of R, G and B images is formed ona-Se-Te layer of the electric charge generating layer on thephotosensitive member.

Photographing procedure was as follows: The above photosensitive memberand the electrostatic information recording medium prepared in theExample 3 were placed face-to-face using PET film (9 μm thick) with R, Gand B portions removed as a spacer. With voltage of 750 V appliedbetween two electrodes of the photosensitive member and theelectrostatic information recording medium (positive electrode on thephotosensitive member side), the optical shutter for 1/60 sec. wasreleased, and outdoor scene was photographed with maximum exposureintensity of 1000 luxes on the light receiving portion.

As the result, positive electrostatic image corresponding to each of theseparated colors of R, G and B were formed on the electrostaticinformation recording medium (size: 25 mm×50 mm).

EXAMPLE 34!

Description is now given on the method to form holographic color filter.

For the photo mask 42 with slits in stripes, a normal photo mask can beused. In the present example, chromium was patterned on a glasssubstrate and was used. As the photosensitive material 41, an materialhaving the resolution required and sensitivity to 3 primary colors canbe used. Dichromate gelatin, photopolymer, etc. may be used. In thepresent example, a silver salt photosensitive material Kodak 649F wasused.

(1) As shown in FIG. 17, photo mask 42 was set on the predeterminedposition on both sides of the photosensitive material 41. Krypton laser(647 nm) was irradiated from the opposite direction as R light, and theinterference pattern by R light was recorded on the photosensitivematerial 41. Next, the photo mask was deviated by the predetermineddistance, and the interference pattern was recorded using argon laser(514 nm) as G light. Further, the photo mask 42 was deviated by thepredetermined distance, and interference pattern was recorded usingargon laser (457 nm) as B light. (Exposure: 60 μJ/cm).

After this triplicate exposure, development was performed for 2 minutesby CWC-2 and bleaching was performed for one minute by PBQ-2. Afterwashing with water for 10 minutes and drying in the air, holographiccolor filter was prepared.

Transmission type and reflection type differ from each other only in thedirection of incident light, and the method to form color hologram isthe same.

(2) The thickness of silver salt photosensitive material changes byswelling and shrinkage when it is processed by D-sorbitol watersolution, for example. Thus, the spacing of interference fringes ofhologram can be changed.

After the above Kodak 649F photosensitive material was immersed andswollen in 11.7% D-sorbitol water solution for one minute, photo mask 42was set at the predetermined positions on both sides of thisphotosensitive material. By irradiating krypton laser (647 nm) fromopposite direction, the green region of the photosensitive material wasexposed to light, and interference pattern was recorded on green region.

Next, after the photosensitive material was immersed and swollen for oneminute in 2% D-sorbitol water solution, photo mask 42 was deviated bythe predetermined distance. The red region on the photosensitivematerial was exposed to the same krypton laser (647 nm), and theinterference pattern was recorded.

Further, after the photosensitive material was immersed and swollen in22.5% D-sorbitol water solution for one minute, photo mask 42 wasdeviated by the predetermined distance. Blue region of thephotosensitive material was exposed to the same krypton laser (647 nm),and the interference pattern was recorded by the same procedure.

After the exposure, development was performed for 2 minutes by CWC-2,and bleaching was performed for one minute by PBQ-2. After washing withwater for 10 minutes and drying in the air, holographic color filter wasprepared.

The holographic color filter thus prepared was placed on a-Sephotosensitive member prepared in the Example 18 as shown in FIG. 32 sothat each of R, G and B images is formed on a-Se-Te layer of theelectric charge generating layer on the photosensitive member.

The photographing procedure was as follows: The above photosensitivemember and the electrostatic information recording medium prepared inthe Example 3 were placed face-to-face using PET film (9 μm thick) withR, G and B portions removed as a spacer. With voltage of 750 W appliedbetween two electrodes of the photosensitive member and theelectrostatic information recording medium (positive electrode onphotosensitive member side), optical shutter was released for 1/60 sec.,and outdoor scene was photographed with maximum exposure intensity of1000 luxes on the light receiving portion.

As the result, positive electrostatic charge image corresponding to eachof R, G and B regions was formed on the electrostatic informationrecording medium (size: 25 mm×50 mm).

EXAMPLE 35! Electrostatic information recording and reproducing methodon the first electrostatic information recording medium

As shown in FIG. 33, single layer organic photosensitive member(PVK--TNF) prepared in the Example 16 and the electrostatic informationrecording medium prepared in the Example 1 were disposed with thesurface of the medium placed face-to-face to the photoconductive surfaceof the above photoconductive layer and grounded. Next, DC voltage of 700V was applied between two electrodes with the photosensitive member sideas positive and the resin layer side as negative.

Under voltage application, exposure was performed for 1 second usinghalogen lamp of 1000 luxes as light source from the side of thephotosensitive member, and the formation of electrostatic latent imagewas completed.

Next, the potential difference between the electrode and the mediumsurface was measured. The surface potential of 100 V was measured on themedium surface by surface potentiometer, and the surface potential onnon-exposed portion was 0 V.

EXAMPLE 36!

Process for recording electrostatic information in the firstelectrostatic information recording medium and reproducing it

The photosensitive member (PVK--TNF) prepared in Example 16 was locatedin opposition to the polyester electrostatic information recordingmedium prepared in Example 10, using as the spacer a 10 μm thickpolyester film. Subsequently, a DC voltage of -600 V was applied betweenboth electrodes with the photosensitive member negatively and theresinous layer positively.

While the voltage was impressed, the recording medium was exposed fromthe photosensitive member to light emanating from a light source halogenlamp at a luminous intensity of 1000 luxes for one second.

As a result of the measurement of surface potentials, the surfacepotential of the recording medium was found to be -150 V by a surfaceelectrometer. However, the unexposed region was found to have a surfacepotential of -35 V.

EXAMPLE 37!

The photosensitive member 9PVK--TNF) of Example 16 and the electrostaticinformation recording medium of Example 14 (a) are laid on top ofanother with the electrode outside, and are then set in a camera. Inorder to provide a space between the photosensitive member and therecording medium, a 10 μm polyester film is disposed as the spaceraround the surface to be exposed to light.

With the photosensitive member's electrode negatively and the recordingmedium positively, a voltage of -700 V was impressed. In that state, theoptical shutter was clicked at an exposure f=1.4 and a shutter speed of1/60 sec., or a voltage was applied for 1/60 sec. at an exposure f=1.4with the shutter held open, thereby photographing a subject outdoors inthe daytime. After the exposure and the application of voltage were putoff, or the application of voltage was put off, the electrophotographicrecording medium was removed out in a bright or dark place, and (1) CRTimaging was carried out by microarea potential reading and (2) imagingwas performed by toner development.

In (1), X-Y axis scanning was carried out with a 100×100 μm probe formeasuring microarea surface potentials to process potential data of 100μm units, and imaging was performed on a CRT by potential brightnessconversion. Formed on the electrostatic information recording medium isan analog potential latent image from a high potential -200 V of theexposed region to a low -50 V of the unexposed region, which could bedeveloped on the CRT at a resolution of 100 μm.

In (2), the removed electrostatic information recording medium wasimmersed in a negatively charged wet toner (black) for 10 seconds,thereby obtaining a positive image. The resolution of the obtained tonerimage was as high as 1 μm.

Color images were photographed in the following manners.

(1) Prismatic Three Plane-Splitting

As illustrated in FIG. 12, the R, G and B filters were disposed on threeplanes of a prism. While the above media were set on the planes, asubject was photographed at f=1.4 and a shutter speed of 1/30 sec.

(2) Color CRT Displaying

The R, G and B latent images were read by scanning in a similar mannerto form on a CRT fluorescences corresponding to the R, G and B latentimages, and images separated into three colors were compounded on theCRT to obtain a color image.

(3) Toner Development

The electrostatic information recording medium subjected to colorseparation and exposure was developed with C (cyan), M (magenta) and Y(yellow) charged negatively with respect to the R, G and B latent imagesto form toner images. Before the toner were dried, paper was put on themedium on which the cyane toner image was formed, and was thenpositively charged by corona. Thereafter, the toner image wastransferred to the paper upon released. While the images were inalignment, the magenta and yellow toners were successively transferredto the same position, whereby a color image is formed on the paper.

EXAMPLE 38!

The photosensitive member (PVK--TNF) of Example 16 was superposed on theelectrostatic information recording medium of Example 14 (a) in oppositerelation through a spacer of a 10 μm thick polyester film. Then, a DCvoltage of -700 V is applied between both electrodes with thephotosensitive member negatively and the insulating layer positively.

It is noted that in the case of the amorphous silicon photosensitivemember, voltage is applied with the photosensitive member negatively,while in the case of the amorphous selenium, voltage is applied with thephotosensitive member positively.

While the voltage was impressed, the recording medium was exposed fromthe photosensitive member to light emanating from a light source halogenlamp at a luminous intensity of 1000 luxes. After the exposure, thevoltage was put off. As a result, a surface potential of -220 V wasmeasured on the exposed region of the recording medium by means of asurface electrometer, while a surface potential of -35 V was obtained onthe unexposed region thereof.

Then, dimethyl silicon oil was used as contact material, and a polyesterfilm was laminated by using dimethyl silicon as the close contact typeadhesive agent to read potentials from above the film. As a result, asurface potential of -220 V was again measured by a surfaceelectrometer. After this polyester film was peeled off, additionalpotential reading indicated that charges were retained in the insulatinglayer.

The recording medium was also similarly exposed to light, while aresolution pattern film was brought in close contact with thephotosensitive member. Thereafter, the recording medium was subjected toX-Y axis scanning with a 50×50 μm probe surface for measuring microareapotentials to process potential data of 50 μm units, which were thendisplayed on a CRT by potential-brightness conversion on an enlargedscale. In consequence, resolution patterns of up to 100 μm wereconfirmed on the CRT. After the exposure, the electrostatic informationrecording medium was allowed to stand at room temperature of 25° C. and35% R.H. for three months. Subsequent similar potential reading byscanning indicated that the obtained resolution patterns were quitesimilar to those just after the exposure.

After the exposure of the resolution pattern, an insulating film waslaminated in place and a resolution of up to 100 μm was obtained on theCRT by reading from above the laminated film.

A subject was photographed with an ordinary camera at an exposure f=1and a shutter speed of 1/60 sec. outdoors in the daytime, while avoltage of -700 V was impressed. After the exposure, the electrostaticinformation recording medium was subjected to X-Y axis scanning with a50×50 μm probe surface for measuring microarea potentials to processpotential data of 50 μm units, which were then displayed on a CRT bypotential-brightness conversion on an enlarged scale. As a result, itwas found that imaging of good gradiation occurred. A similar film asstated above was laminated on the electrostatic information recordingmedium to measure imaging from above the laminated film. In consequence,it was found that imaging having gradiation quite similar to that in theabsence of any laminated film occurred.

EXAMPLE 39!

FIG. 66 is a graphical view showing the charge retainability of theelectrostatic information recording medium of Example 14 (a), in whichthe results of the surface potentials, as measured, are plotted with thetime elapsed.

A line A refers to the recording medium allowed to stand at atemperature of 25° C. and a humidity of 30%. Even after the lapse ofthree months, the surface charges on the recording medium were notattenuated. A line B refers to the recording medium allowed to stand ata temperature of 40° C. and a humidity of 75%. After the lapse of oneweek, the attenuation of the surface charges was barely about 25%.

EXAMPLE 40! Photosensitive Member Provided with Discharge-ReinforcingLayer

The transparent electrode to be used was obtained by providing a 1000 Åthich In₂ O₃ -SnO₂ (ITO) film on a glass substrate of 1 mm in thicknessby sputtering. A 10 μm thick a-Se film was then formed on the ITO filmby vacuum vapor-deposition (10⁻⁵ Torr, resistance heating) to constructa photoconductive material.

TiC was further formed to a thickness of 500 Å on the a-Se layer bysputtering (10⁻² Torr, argon plasma) to form a discharge-reinforcinglayer. Thus, the final photosensitive member was formed using the abovephotoconductive material.

In order to obtain the electrostatic information recording medium, onthe other hand, aluminium was formed to a thickness of 1000 Å on a glasssubstrate of 1 mm in thickness by vacuum vapor deposition (10⁻⁵ Torr,resistance heating), and a silicone resin layer (CR-15, 2%, TSR-144,available from Toshiba Silicone) was provided by spinner coating (with a10% toluenexylene solution and at 1000 rpm×10 sec.), followed by 1 hourheating at 150° C., thereby forming an insulating layer having a filmthickness of 6 μm.

Both the members were arranged through an air gap of 10 μm with the filmsides opposite to each other.

Referring to voltage application and exposure, a voltage of 400 V wasapplied between both electrodes while using the photosensitive member'selectrode as the positive electrode. In that state, a half area of thephotosensitive member was exposed through a mask to light emanating froma halogen lamp at 10 luxes for 1 second. After the exposure, the voltagewas cut off, followed by the removal of the electrostatic informationrecording medium. Afterwards, the potentials stored on the exposed andunexposed regions were found to be 150 V and 30 V, respectively, bymeasurement with a surface electrometer.

On the other hand, a photosensitive member comprising the a-Se layeralone, i.e., which was not provided with any discharge-reinforcinglayer, was impressed with voltage and exposed to light under similarconditions. As a consequence, no storage of potentials was observed onboth the exposed and unexposed regions.

When this photosensitive member was impressed with a voltage of 700 Vand exposed to light in a similar manner as mentioned above, it wasobserved that the surface potentials were 170 V on the exposed regionand 40 V on the unexposed region, these numerical values beingsubstantially equal to the accumulated potentials obtained when thedischarge-reinforcing layer was provided.

From the foregoing, it has been found that the voltage to be externallyimpressed can be effectively reduced by the provision of such adischarge-reinforcing layer.

EXAMPLE 41!

The discharge-reinforcing layer of Example 40 was formed on the a-Selayer to a thickness of 300 Å by EB vapor deposition (10⁻⁵ Torr),provided however that CeB₆ was used in place of TiC. When theelectrostatic information recording medium was subjected to similarvoltage application and exposure, it was observed that surfacepotentials of 120 V and 40 V were obtained on the exposed and unexposedregions, respectively.

EXAMPLE 42!

An SnO₂ film was formed on an 1 mm thick glass substrate to a thicknessof 2000 Å by sputtering to prepare a transparent electrode. A 5%(calculated as solid) solution of an 1:1 (molar ratio) mixture ofpolyvinyl carbazole (available from Anan Koryo) and2,4,7-trinitrofreonone (available from Junsei Chemical) in chloroformwas then spread on the above substrate with a doctor blade (with a gapwidth of 200 μm). Subsequent one hour drying at 60° C. gave aphotoconductive layer having a film thickness of 15 μm.

With an LaB₆ target, a 300 Å thick LaB₆ film was further sputtered onthe above photoconductive layer to prepare a discharge-reinforcinglayer.

An electrostatic information recording medium similar to that of Example40 was used. For the impression of voltage and exposure, a voltage of400 V was applied between both electrodes, while the photosensitivemember's electrode was used as the negative electrode. As a result ofthe exposure of the recording medium to light under exposure conditionssimilar to those applied in Example 40, surface charges of -180 V and-55 V were obtained on the exposed and unexposed regions, respectively.

For the purpose of comparison, similar voltage impression and exposurewere carried out with only the PVK--TNF layer, i.e., on which no LaB₆film was formed. The result was that no charge was obtained at all onthe electrostatic information recording medium. On the other hand, theexternally applied voltage was increased to -1000 V. The results werethat charges of -200 V and -80 V were obtained on the exposed andunexposed regions, respectively.

EXAMPLE 43!

TiO₂ was formed on the inorganic photosensitive member of amorphoussilicon (a-Si:H) prepared in Example 17 to a thickness of 500 Å bysputtering to form a discharge-reinforcing layer. The electrostaticinformation recording medium prepared in Example 40 was impressed with avoltage of -500 V, while the photosensitive member's electrode was usedas the negative electrode, and was then exposed to light emanating froma halogen lamp at 10 luxes for 10⁻³ sec. The results were that surfacepotentials of -180 V and -110 V were measured on the exposed andunexposed regions, respectively.

On the other hand, similar experiment was carried out with aphotosensitive member on which no discharge-reinforcing layer wasformed. No surface voltage was observed at the same voltage. When theapplied voltage was increased to, e.g., -800 V, the same potentials of-80 V appeared on both the exposed and unexposed regions, so that noimage of the exposed region was formed. Hence, it was found that by theprovision of a discharge-reinforcing layer, not only could the effectiveexternal voltage be decreased but the responsibility to light could alsobe increased.

EXAMPLE 44! Process for recording electrostatic information in thesecond electrostatic information recording medium and reproducing it

With a micropipet, ω-phenylic acid was added dropwise in water to form amonomolecular film of ω-phenylic acid on the surface of the water. Onthe other hand, aluminium was vapor-deposited on an 1 mm thick glasssubstrate to form an electrode layer having a thickness of 1000 Å. Tenmonomolecular films, each as mentioned just above, were laminated on theelectrode surface at a surface pressure of 30 dynes/cm² and a drawing-uprate of 1 cm/min. to obtain a film having a thickness of 200 Å.Subsequent air-drying gave the electrostatic information recordingmedium 3 according to the present invention.

This recording medium 3 is located in opposition to the photosensitivemember 1 prepared in Example 16 through a void of about 10 μm defined bya 10 μm thick polyester film used as the spacer. Then, a DC voltage of-500 V is applied between both electrodes with the photosensitive membernegatively and the recording medium positively. In that state, therecording medium is exposed from the back side of the photosensitivemember to light emanating from a light source halogen lamp at a luminousintensity of 1000 luxes for 1 second. After the completion of theexposure, the voltage is cut off. The formation of an electrostaticlatent image is then completed by the removal of the recording medium 3.As a result, the charge retaining layer was found to have a surfacepotential of -20 V by measurement with a surface electrometer. However,the surface potential of the exposed region was 0 V.

Similar exposure was carried out while a resolution pattern film wasbrought in close contact with the back side of the photosensitivemember. Afterwards, the electrostatic information recording medium wassubjected to X-Y axis scanning with a 50×50 μm probe surface formeasuring microarea potentials to process potential data of 50 μm units,which were then displayed on a CRT by potential-brightness conversion onan enlarged scale. As a result, resolution patterns of up to 100 μm wereconfirmed on the CRT. After the exposure, the electrostatic informationrecording medium was allowed to stand at room temperature of 25° C. and35 R.H. for three months for similar potential reading by scanning. As aconsequence, resolution pattern displays quite similar to those justafter the exposure were obtained.

For alternative exposure, a subject was photographed with an ordinarycamera at an impression voltage of -500 V, an exposure f=1.4 and ashutter speed of 1/60 sec. outdoors in the daytime. After the exposure,the recording medium was subjected to X-Y axis scanning with a 50×50 pmprobe surface for measuring microarea potentials to process potentialdata of 50 μm units, which were then displayed on a CRT bypotential-brightness conversion on an enlarged scale. As a result,imaging having gradiation occurred.

EXAMPLE 45!

Octadecyl maleate was used as the material for an LB film, and anelectrostatic information recording medium having a film thickness of300 Å was prepared with similar substrate and process to those describedin Example 44. For the estimation of the charge retainability of thisrecording medium, a surface potential of 50 V was given to the medium'ssurface by corona charging (which involves applying high voltage to acorona wire to give the discharged ions to an object along theelectrified). Under such conditions expressed in terms of roomtemperature (25° C., 35% R.H.), 40° C. (dry) and 60° C. (dry), thesurface potential attenuation characteristics were estimated. Theresults were that no potential change was found whatsoever at roomtemperature even after five months, and the potentials existed in stablefor two months at 40° C. (dry) and up to as long as 15 days at 60° C.(dry).

For the purpose of comparison, in place of the LB film, a 10% by weightsolution of a polyester resin (Vylon 200 available from Toyobo) inchloroform was coated to a thickness of 2 μm (on dry basis) with adoctor blade to form a charge retaining layer, of which similarestimation was then made. The results were that the surface potentialattenuated to 40 V even after allowed to stand at room temperature forone day and dropped to 10 V at 40° C. even after the lapse of one day.At 60° C., no potential could be measured even after the lapse of oneday.

EXAMPLE 46!

An electrostatic information recording medium comprising octadecylmaleate was used. After a 2 μm resolution pattern had been formed on thesurface of the charge retaining layer in such a manner as described inExample 44, the recording medium was allowed to stand at 40° C. (dry)for one day. Thereafter, toner development was carried out with a wettoner of (-) polarity. The resulting toner image reproduced faithfullythe resolution pattern, and toner development having a resolution of 2μm occurred.

For the purpose of comparison, similar estimation was made with a mediumin which the charge retaining layer was formed of a polyester resin. Theresults were that the concentration of toner development dropped due toa surface potential attenuation and, at the same time, the resolution ofthe toner image itself was so reduced that the image faded.

EXAMPLE 47! Third Electrostatic Information Recording Medium (ThermalElectret)

Aluminium was deposited on a 20 μm thick polyvinylidene fluoride film toa thickness of 1000 Å by vacuum vapor deposition (10⁻⁶ Torr, resistanceheating) to form an electrostatic information recording medium, on whichan electrostatic latent image was formed with a photoconductive memberof the function-separated type.

A hot plate (3×3 cm) was first brought in contact with the aluminiumsubstrate side of the recording medium to heat the recording medium to180° C. Immediately after heating, the photosensitive member was locatedin opposition to the recording medium through an air gap of 10 μm inface-to-face relationship. A voltage of -550 V was applied between bothelectrodes (with the photosensitive member's electrode negatively),followed by exposure. This exposure was carried out at 10 luxes from theback side of the photosensitive member for a character patternmanuscript for 1 second, using a halogen lamp as the light source.

Afterwards, the film was air-cooled. The results were that a potentialof -150 V was measured on the exposed (character) region, but nopotential was measured on the unexposed region. Water was added dropwiseto the film on which the charged pattern was formed, which film was thenremoved out to measure its potential. The result was that a potential of-150 V was again obtained on the exposed region. On the other hand, asimilar electrostatic information recording medium was forcedly chargedon its surface at -150 V by corona discharge. Thereafter, water wasadded dropwisely to the medium, which was then removed out. As a result,it was found that the exposed region, previously charged to -150 V, wascompletely deprived of charge. Hence, it was noted that in the processof charging with the application of heat, polyvinylidene fluoride wassubjected to internal polarization, resulting in the formation of anelectret.

With the thus formed electret used as an electrostatic informationrecording medium, such potential reading as mentioned above waspossible.

EXAMPLE 48! Third Electrophotographic Information Recording Medium(Optical Electret)

Aluminium was laminated on an 1.1 mm thick glass support to a thicknessof 1000 Å by sputtering to make a substrate, and zinc sulfide was thendeposited (at 10⁻⁵ Torr and by resistance heating) on the resultingaluminium layer to a film thickness of about 1.5 μm. An ITO surfaceformed on glass was located in opposition to the surface of the zincsulfide layer through an air gap of 10 μm, while a voltage of +700 V wasapplied between both electrodes (with the Al electrode negatively). Inthat state, exposure was carried out from the ITO substrate in a similarmanner as described in Example 47. The results were that a potential of+80 V was measured on the exposed region, but not potential was found onthe unexposed region. Again, similar water droplet experiment as inExample 47 was carried out. After the removal of water droplet, nopotential change was found. Thus, there was obtained an electret inwhich charges were accumulated.

With the thus formed optical electret used as an electrostaticinformation recording medium, such potential reading as mentioned abovewas possible.

EXAMPLE 49! Fourth Electrostatic Information Recording Medium

An SiO₂ film was sputtered on a glass substrate vapor-deposited with1000 Å aluminium to form a charge retainability-reinforcing layer 10having a film thickness of 100 Å. Further coated on that film was amixed solution composed of 1 g of a polyester resin (Vylon 200) and 10 gof chloroform by doctor blade coating to form an insulating layer havingno charge injection. Subsequent 1 hour drying at 100° C. gave aninsulating layer 11 having a film thickness of 10 μm.

EXAMPLE 50!

In the process for making an electrostatic information recording medium,as described in Example 49, the order of lamination of the chargeretainability-reinforcing layer and the insulating layer having nocharge injection was reversed. In other words, a mixed solution of 1 gof a polyester resin (Vylon 200) and 10 g of chloroform was first coatedon a glass substrate vapor-deposited with 1000 Å thick aluminium bydoctor blade coating, and was then dried at 100° C. for 1 hour to formthe insulating layer 11. Subsequently, an SiO₂ film having a filmthickness of 100 Å was sputtered as the charge retainability-reinforcinglayer 10 on the insulating layer.

EXAMPLE 51!

A mixed solution composed of 1 g of a polyester resin (Vylon 200) and 10g of chloroform was coated on a glass substrate vapor-deposited with1000 Å thick aluminium by doctor blade coating, and was then dried at100° C. for 1 hour to form an insulating layer having a thickness of 10μm. On the other hand, ω-phenylic acid was added dropwise in water by amicropipet to form a monomolecular film of ω-phenylic acid on thesurface of the water. Five monomolecular films, each as mentioned justabove, were laminated on the above polyester resinous layer at a surfacepressure of 30 dynes/cm² and a drawing-up speed of 1 cm/min. to a filmthickness of 100 Å, followed by air-drying.

EXAMPLE 52!

A mixed solution of 1 g of a polyester resin (Vylon 200) and 10 g ofchloroform was coated by doctor blade coating, on a glass substrate with1000 Å thick vapor-deposited aluminium, and was then dried at 100° C.for 1 hour, followed by further vapor-deposition of polyethylene to afilm thickness of 100 Å.

EXAMPLE 53!

The single layer organic photosensitive member of Example 16 was locatedin opposition to the electrostatic information recording medium 3prepared in Example 49 through an air gap of 10 μm defined by a 10 μmthick polyester film used as the spacer. Then, a DC voltage of -700 Vwas applied between both electrodes with the photosensitive membernegatively and the recording medium positively. In that state, exposurewas carried out from the back side of the photosensitive member for 1second, while using as the light source a halogen lamp having a luminousintensity of 1000 lux. After the completion of the exposure, the voltagewas shut off. A surface potential of -200 V was measured on the exposedregion of the recording medium by a surface electrometer, while asurface potential of 0 V was obtained on the unexposed region thereof.

Similar exposure was carried out, while a resolution pattern film wasbrought in close contact with the back side of the photosensitivemember. Thereafter, the electrostatic information recording medium wassubjected to X-Y axis scanning with a 50×50 μm probe surface formeasuring microarea potentials to process potential data of 50 μm units,which were then displayed on a CRT by potential-brightness conversion onan enlarged scale. As a result, resolution patterns of up to 100 μm wereconfirmed on the CRT. After the exposure, the recording medium waspermitted to stand at room temperature of 25° C. and 35 R.H. for threemonths. Afterwards, similar reading by scanning indicated thatresolution pattern displays quite similar to those just after theexposure were obtained.

For alternative exposure, a subject was photographed with an ordinarycamera at an impression voltage of -700 V, an exposure f=1.4 and ashutter speed of 1/60 sec. outdoors in the daytime. After the exposure,the electrostatic information recording medium was subjected to X-Y axisscanning with a 50×50 μm probe surface for measuring microareapotentials, which are then displayed on a CRT by potential-brightnessconversion on an enlarged scale. As a result, imaging having gradiationwas found to occur.

Color images were photographed in the following manners.

(1) Prismatic three-plane splitting

As illustrated in FIG. 12, the R, G and B filters were disposed on threeplanes of a prism, and the same media as described above were set on theplanes to photograph a subject at an exposure f=1.4 and a shutter speedof 1/30 sec.

(2) Color CRT displaying

The R, G and B latent images were read by scanning in a similar mannerto form on a CRT fluorescences corresponding thereto, and the resultingimages separated into three colors were compounded on the CRT to obtaina color image.

EXAMPLE 54! Fifth Electrostatic Information Recording Medium

A solution of 10 g of a rosin ester resin (Stayberite Ester 10)dissolved in 90 g of n-butyl alcohol was coated on a glass substratevapor-deposited with 1000 Å thick aluminium by spinner coating (at 1000rpm for 90 seconds). In order to evaporate off the solvent, thesubstrate was permitted to stand at 60° C. for 1 hour. As a result, anevenly coated film having a film thickness of 2 μm was formed.

Amorphous selenium was vapor-deposited on this medium under thefollowing conditions.

The medium is first fixed to a substrate holder in a vacuum chamber,while the glass surface comes in contact therewith. This substrateholder can be heated (by means of a heater) such that the substratemedium is heated to 100° C. during vapor deposition. Vapor deposition iscarried out by ordinary resistance heating. In this case, selenium wasvapor-deposited at a degree of vacuum as low as 0.1 Torr. As a result,selenium is deposited in the form of microparticles in the rosin esterresin layer to a depth of 0.1 μm, said particles having a mean particlesize of about 0.5 μm. Thus, there was obtained an electrostaticinformation recording medium as illustrated in FIG. 4 (a).

EXAMPLE 55!

As a resinous layer, a thermosetting epoxy resin (Aduldite availablefrom Ciba Geigy) was coated on a similar substrate as used in Example 54by spinner coating. in order to evaporate off the solvent, the substratewas permitted to stand at 60° C. for 30 minutes. Then, while the resinremained uncured, selenium was deposited on the resinous layer at asimilar degree of vacuum as applied in Example 54. In this case,however, selenium was deposited at normal temperature without heatingthe substrate holder. As a result, the particulate layer was formed inthe vicinity of the interior surface of the epoxy resin, as was the casewith the rosin ester resin. In order to cure the epoxy resin, thesubstrate was thereafter permitted to stand at 120° C. for 1 hour. As aresult, the resinous layer was cured to give a 15 μm thick electrostaticinformation recording medium in which selenium particles existed.

EXAMPLE 56!

As a resinous layer, a modified acrylate resin (VDAL-388 available fromDainichi Seika) that was an ultraviolet curable resin was coated on asimilar substrate as used in Example 54 by spinner coating (at 1000 rpmfor 20 seconds) to provide thereon an uncured resinous layer. In thatstate, the vapor deposition of selenium was carried out under similarvacuum conditions as applied in Example 54. Thereafter, the substratewas removed out from within the chamber, and was then irradiated withultraviolet rays emanating from an ultraviolet lamp (a 365 nm peak lamp)in an quantity of light of 50 mJ/cm² to cure the resinous layer. As aresult, there was obtained an electrostatic information recording mediumcomprising a resinous layer of 8 μm in thickness and a solenium layerbeing present in the form of a single layer located about 0.5 μm belowthe surface of the acrylate resinous layer with the selenium particleshaving a mean particle size of 0.3 μm.

EXAMPLE 57!

A 50% solution of a silicone resin (TSR-144 available from ToshibaSilicone and containing 1% of a curing agent CR-15) diluted with xylenewas coated on an 1 mm thick glass substrate vapor-deposited with 1000 Åthick aluminium by spinner coating (at 1000 rpm for 20 seconds).Thereafter, the solvent was evaporated off at 150° C. for 1 hour to curethe resin. As a result, an evenly coated film having a film thickness of7 μm was formed.

Amorphous selenium was formed on this medium under the followingconditions by vapor deposition. The medium is first fixed to a substrateheating holder within a vacuum chamber, while the glass surface comes incontact therewith. During vapor deposition, the substrate was heated toa temperature of 90° C. to vapor-deposit selenium at a degree of vacuumas low as 1 Torr. As a result, selenium was finely divided to a particlesize of about 1 μm and laminated on the silicone resin in a single layerstate.

Then, the material to be deposited was changed from selenium to apolyethylene (having a degree of polymerization of -20000). At a degreeof vacuum as high as 1×10⁻⁵ Torr, a 0.1 μm polyethylene vapor-depositedfilm was formed on the selenium layer by resistance heating, thusresulting in the formation of an electrostatic information recordingmedium in which the granular layer of selenium was present within theresinous layer.

EXAMPLE 58!

While the material to be deposited was changed from selenium to gold,deposition was carried at a low degree of vacuum under similarconditions as applied in Example 54. As a result, there was obtained anelectrically conductive particle type of electrostatic informationrecording medium in which gold microparticles having an average particlesize of 0.2 μm were in the form of a single layer located 0.1 μm belowthe surface of the Stayberite resin.

EXAMPLE 59!

Aluminium was vapor-deposited on one side of a 12.5 μm thick fluorinefilm (an FEP film available from Daikin Kogyo) to obtain a substrate.Under similar vapor deposition conditions as applied in Example 42,selenium particles were vapor-deposited on the surface of the film. As aresult, a uniform particulate layer of selenium having a particle sizeof about 0.4 μm was formed in a single layer state. Then, furthersputtered on this selenium layer was a Teflon target (available fromKyodo International) at an argon pressure of 3 mTorr and a power densityof 7 W/cm² with a sputter (an RF magnetron sputter) to form an about1000 Å thick Teflon resin layer on the selenium layer. As a result, afilm-like electrostatic information recording medium was obtained.

EXAMPLE 60!

An organic photoconductive material poly-N-vinyl carbazole (PVK: Tubicol210 available from Anan Koryo) was vapor-deposited under vacuum on thesilicone resin (TSR-144) substrate (a glass substrate vapor-depositedwith 1000 Å thick aluminium) prepared in Example 57 under the followingconditions. Without applying heat to the substrate, resistance heatingwas carried out at normal temperature and a degree of vacuum of 10⁻³Torr. As a result, PVK was laminated on the silicone resin in theparticulate form having a mean particle size of about 5 μm. Furthersputtered on this PVK layer was a Teflon target (available from KyodoInternational) at an RF pressure of 3 mTorr and a power density of 7W/cm² with a sputter (an RF magnetron sputter) to form an about 2000 Åthick Teflon resin layer, thereby making an electrostatic informationrecording medium.

EXAMPLE 61!

A 50% solution of silicon resin (TSR-144 available from Toshiba Siliconeand containing 1% of a curing agent CR-15) diluted with xylene wascoated on a 1 mm thick glass substrate vapor-deposited with 1000 Å thickaluminium by spinner coating (at 1000 rpm for 20 seconds). Thereafter,the solvent was evaporated off at 150° C. for 1 hour to cure thesilicone resin. As a result, there was formed a silicone resin layerhaving a film thickness of 7 μm.

Then, 10 g of a rosin ester resin (Steberite Ester 10) and 10 g of zincoxide (having a mean particle size of 10 μm) were mixed with 80 g ofn-butyl alcohol, and the mixture was put with 100 g of glass beads (3mmφ) in a stainless-made cylindrical vessel of 300 ml in volume,followed by lidding. The solution was then dispersed with a vibrationtype dispersing machine (Red Devil) for 2 hours. The solution wasremoved out, and the zinc oxide layer was then coated on the siliconeresin layer by spinner coating (at 500 rpm for 60 seconds), followed bydrying at 60° C. for 3 hours. As a result, there was formed a laminatedtype of electrostatic information recording layer including a 3 μm thickdispersed layer, as illustrated in FIG. 4 (b).

EXAMPLE 62!

The zinc oxide-resin dispersed solution prepared in Example 61 wascoated directly on an aluminium vapor-deposited substrate with a whaler(at 200 rpm for 30 seconds), followed by drying at 60° C. for 3 hours.As a result, there was formed a dispersed type of electrostaticinformation recording medium having a film thickness of 15 μm, asillustrated in FIG. 4 (c).

EXAMPLE 63!

The single layer organic photosensitive member (PVK--TNF) of Example 16is located in opposition to the electrostatic information recordingmedium prepared in Example 54 through a spacer of a 10 μm thickpolyester film, and a DC voltage of -700 V is applied between bothelectrodes with the photosensitive member negatively and the resinouslayer positively. While the voltage is impressed, exposure is carriedout from the photosensitive member for 1 second, using as the lightsource a halogen lamp having a luminous intensity of 1000 luxes. Afterthe exposure, the recording medium is removed out and exposed on itsentire surface to light, whereby the formation of an electrostaticlatent image is completed.

As a consequence, a surface potential of -100 V was measured on theexposed region of the recording medium by a surface electrometer, whilea surface potential of 0 V was obtained on the unexposed region thereof.

Prior to overall exposure, a surface potential of -110 V was measured onthe exposed region, when the surface potential of the electrostaticinformation recording medium was measured in a dark place. It was thusfound that charges were accumulated in the selenium particles by overallexposure.

Similar exposure was then carried out, while a resolution pattern filmwas brought in close contact with the glass substrate of thephotosensitive member. Thereafter, the electrostatic informationrecording medium was subjected to X-Y axis scanning with a 50×50 μmprobe surface for measuring microarea potentials to process potentialdata of 50 μm units, which were then displayed on a CRT bypotential-brightness conversion on an enlarged scale. As a result,resolution patterns of up to 100 μm were confirmed on the CRT. After theexposure, the recording medium was permitted to stand at roomtemperature of 25° C. and 35% R.H. for 3 months. As a result ofsubsequent potential reading by scanning, resolution pattern displaysquite similar to those just after the exposure were obtained.

For alternative exposure, a subject was photographed with an ordinarycamera at an impression voltage of -700 V, an exposure f=1.4 and ashutter speed of 1/60 sec. outdoors in the daytime. After the exposure,the electrostatic information recording medium was subjected to X-Y axisscanning with a 50×50 μm probe surface for measuring microareapotentials to process potential data of 50 μm units, which were thendisplayed on a CRT by potential-brightness conversion on an enlargedscale. As a result, imaging having gradiation occurred.

Color images were photographed in the following manners.

(1) Prismatic three-plane splitting

As illustrated in FIG. 12, the R, G and B filters were disposed on threeplanes of a prism, and the same media as mentioned above were set on theplanes to photograph a subject at f=1.4 and a shutter speed of 1/30 sec.

(2) Color CRT displaying

The R, G and B latent images were read by scanning in a similar mannerto form on a CRT fluorescences corresponding thereto, and the imagesseparated into three colors were then compounded on a CRT to obtain acolor image.

Table 1 shows the charge retainability of the electrostaticinformationrecording media of Examples 54 to 62, as expressed in terms of thesurface potentials measured with the lapse of time. For the purpose ofcomparison, the surface potentials with time of electrostaticinformation recording media A and B consisting only of single rosinester and silicone resin layers are also tabulated.

                  TABLE 1                                                         ______________________________________                                        Estimation of Stability with Time of Internally Accumulated Cahrges           Ex.  Initial pot.                                                                           Initial pot.                                                                           1-day stor.                                                                           7-day stor.                                                                           30-day stor.                           Nos. (V) (1*) (V) (2*) (60° C., dry)                                                                  (60° C., dry)                                                                  (60° C., dry)                   ______________________________________                                        39   -100     -100      -85    -70     -55                                    A    -105     -105      -40       0       0                                   40    -80      -75      -60    -45     -30                                    41   -140     -120     -100    -85     -50                                    42   -150     -135     -130    -115    -85                                    B    -155     -155     -130    -50        0                                   43   -100     -100      -90    -65     -40                                    44   -130     -115     -115    -100    -70                                    45   -120     -110     -100    -85     -50                                    46   -165     -140     -120    -80     -55                                    47   -180     -170     -150    -105    -65                                    ______________________________________                                         (1*): Initial potentials of the exposed regions before overall exposure.      (*2): Initial potentials of the exposed regions after overall exposure.       Note that the photosensitive members used were all PVK  TNF of Example 12     with external application of a voltage of -700 V.                        

EXAMPLE 64! Sixth Electrostatic Information Recording Medium

An aluminium electrode was laminated on a 1 mm thick glass substrate toa film thickness of 1000 Å by vacuum vapor deposition (10⁻⁵ Torr).Coated thereon was spread a 50% solution of a silicone resin (TSR-144,1% CR-15, available form Toshiba Silicone) in xylene by spinner coating(at 1000 rpm for 30 sec.), which was in turn dried at 150° C. for 1 hourfor the provision of an insulating film having a film thickness of 7 μm.Then, the substrate was heated to 100° C. with a heater plate. In thatstate, selenium was vapor-deposited on the substrate at a low degree ofvacuum (3 Torr) for 60 seconds, thereby providing on the silicone layera crystalline granular layer of selenium having a mean diameter size of0.5 μm.

After removed out from the vapor depositor, a 5% solution of polyvinylcarbazole (PVK: Tubicol 210 available from Anan Koryo) in chloroform wasspread on the amorphous granular layer of selenium by spinner coating(at 1000 rpm for 30 seconds), and was then dried at 60° C. for 1 hour toobtain a charge transport layer having a film thickness of 10 μm. Inthis manner, an electrostatic information recording medium as shown inFIG. 5 (a) was formed.

EXAMPLE 65!

As a resinous layer, an epoxy resin (Aduldite available from Ciba Geigy)that was a thermosetting resin was spinner-coated on a similar substrateas used in Example 49. The epoxy resin was then cured at 120° C. for 1hour to form a resinous layer having a film thickness of 15 μm, on whicha substrate was deposited in a room temperature state at a similardegree of vacuum as applied in Example 49. As a result, amorphousselenium was formed on an insulating layer.

After removed out from the vapor depositor, a 5% solution of polyvinylcarbazole (PVK: Tubicol 210 available from Anan Koryo) in chloroform wasspread on the amorphous granular layer of selenium by spinner coating(at 1000 rpm for 30 seconds), and was then dried at 60° C. for 1 hour toobtain a charge transport layer having a film thickness of 10 μm. Inthis manner, an electrostatic information recording medium according tothe present invention was formed.

EXAMPLE 66!

As a resinous layer, a modified acrylate resin (VDAL-383 available fromDainichi Seika) that was an ultraviolet curable resin was spinner-coated(at 1000 rpm for 20 seconds) on a similar substrate as used in Example64, and was then irradiated with ultraviolet rays emitted from anultraviolet lamp (a 365 nm peak lamp) at a dosage of 50 mJ/cm² to curethe resinous layer. Then, the vapor deposition of selenium was carriedout under similar low vacuum conditions as applied in Example 64. As aresult, the selenium layer was laminated on the acrylate resin layerhaving a thickness of 8 m in the form of a single granular layer havinga mean granular size of 0.3 μm.

After removed out from the vapor depositor, a 5% solution of polyvinylcarbazole (PVK: Tubicol 210 available from Anan Koryo) in chloroform wasspread on the amorphous granular layer of selenium by spinner coating(at 1000 rpm for 30 seconds), and was then dried at 60° C. for 1 hour toobtain a charge transport layer having a film thickness of 10 μm. Inthis manner, an electrostatic information recording medium according tothe present invention was formed.

EXAMPLE 67!

In lieu of the polyvinyl carbazole used in Example 64, a solution of 5 gof a hydrazone charge transport agent (CTC-191 available from AnanKoryo) and 5 g of polycarbonate (Upiron available from Nippon GasChemical) dissolved in 90 g of 1,2-dichloroethane was spread on thecrystalline granular layer of selenium by spinner coating (at 1000 rpmfor 10 seconds), and was then dried at 60° C. for 1 hours to obtain acharge transport layer of 10 μm in thickness.

EXAMPLE 68!

While the material for vapor deposition was changed from selenium togold, low-vacuum vapor deposition was carried out by crucible resistanceheating under similar conditions as applied in Example 64. As a result,black gold microparticles having a mean particle size of 0.2 μm wereformed on the silicone resin layer in a single layer state. Then, a 10μm thick charge transport layer comprising a polyvinyl carbazole similarto that used in Example 64 was laminated on the gold layer to obtain anelectrically conductive granular type of electrostatic informationrecording medium of the structure wherein charges were internallyaccumulated.

EXAMPLE 69!

Aluminium was vapor-deposited on one side of a fluorine film (an FEPfilm available from Daikin Kogyo) to a thickness of 1000 Å to form asubstrate. Under similar vapor deposition conditions as applied inExample 64, selenium particles were vapor-deposited on the surface ofthe film. As a result, a single layer of a uniform granular layer havinga granular size of about 0.4 μm was formed. A 10 μm thick chargetransport layer comprising a polyvinyl carbazole similar to that used inExample 64 was then coated with a blade coater having a gap width of 200μm.

EXAMPLE 70!

In the deposition of selenium in Example 64, the deposition time wasincreased from 60 seconds to 300 seconds. As a result, plural layers ofcrystalline selenium were formed on the silicone resin layer. This wasconfirmed under an optical microscope. In a similar manner, thepolyvinyl carbazole was later laminated.

EXAMPLE 71!

A 50% solution of a silicone resin (TSR-144 available from ToshibaSilicone and containing 1% of a curing agent CR-15) diluted with xylenewas spinner-coated (at 1000 rpm for 20 seconds) on a 1 mm thick glasssubstrate vapor-deposited with 1000 Å thick aluminium, and was thendried at 150° C. for 1 hour to evaporate off the solvent and cure theresin. As a result, a silicone resin layer having a film thickness of 7μm was formed.

Subsequently, 10 g of a rosin ester resin (Stayberite Ester 10) and 10 gof zinc oxide (having a mean particle size of 10 μm) were mixed with 80g of n-butyl alcohol, and the mixture was introduced with 100 g of glassbeads (3 mmφ) in a stainless-made cylindrical vessel of 300 ml involume, followed by lidding. The mixture was then dispersed with avibration type dispersing machine (Red Devil) for 2 hours. After removedout from within the vessel, the zinc oxide dispersed layer was coated onthe silicone resin by spinner coating (at 500 rpm for 60 seconds), andwas then dried at 60° C. for 3 hours. As a result, the film thickness ofthe dispersed layer was 3 μm. Then, a 10 μm thick charge transport layersimilar to that used in Example 64 was laminated to obtain a medium asshown in FIG. 5 (b).

EXAMPLE 72!

The zinc oxide/resin dispersed solution prepared in Example 71 wascoated directly on an aluminium substrate with a whaler (at 200 rpm for30 seconds), and was thereafter dried at 60° C. for 3 hours for thelamination of a zinc oxide-dispersed resin layer having a film thicknessof 15 μm. Then, a 10 μm thick charge transport layer similar to thatused in Example 64 was laminated on this resin layer to form a dispersedtype of electrostatic information recording medium as illustrated inFIG. 5 (c).

EXAMPLE 73!

The single layer organic photosensitive member (PVK--TNF) prepared inExample 16 was arranged with the electrostatic information recordingmedium prepared in Example 64 in such a manner that the charge transportlayer's surface of the recording medium was grounded in opposition tothe photoconductive layer's surface, using as the spacer a 10 μm thickpolyester film. Then, a DC voltage of -700 V was applied between bothelectrodes with the photosensitive member negatively and the resinouslayer positively.

While the voltage was impressed, exposure was carried out from thephotosensitive member for 1 second, using as the light source a halogenlamp having a luminous intensity of 1000 luxes. After the completion ofthe exposure, the electrostatic information recording medium was removedout and exposed on its overall surface to light, whereby the formationof an electrostatic latent image was completed.

As a result, a surface potential of -100 V was measured on the exposedregion of this recording medium by a surface electrometer, while asurface potential of 0 V was obtained on the unexposed region thereof.

When the surface potential of the electrostatic information recordingmedium was measured in a dark place prior to overall exposure, a surfacepotential of its exposed region was found to be -110 V. It was thusappreciated that charges were accumulated in the selenium particles bythe overall exposure.

Then, similar exposure was performed while a resolution pattern film wasbrought in close contact with the glass substrate of the photosensitivemeber. As illustrated in FIG. 53, the electrophotographic informationrecording medium was thereafter subjected to X-Y axis scanning with a50×50 μm probe surface for measuring microarea potentials to processpotential data of 50 μm units, which were then displayed on a CRT bypotential-brightness conversion on an enlarged scale. As a result,resolution patterns of up to 100 μm were confirmed on the CRT. After theexposure, the electrostatic information recording medium was allowed tostand at room temperature of 25° C. and 35% R.H. for three months.Subsequent potential reading by scanning indicated that resolutionpattern displays quite similar to those just after the exposure wereobtained.

For alternative exposure, a subject was photographed with an ordinarycamera at an impression voltage of -700 V, an exposure f=1.4 and ashutter speed of 1/60 sec. outdoors in the daytime. After the exposure,the electrostatic information recording medium was subjected to X-Y axisscanning with a 50×50 μm probe surface for measuring microareapotentials to process potential data of 50 μm units, which were in turndisplayed on a CRT by potential-brightness conversion on an enlargedscale. As a result, imaging having gradiation occurred.

Color images were photographed in the following manners.

(1) Prismatic three-plane splitting

As illustrated in FIG. 12, the R, G and B filters were disposed on threeplanes of a prism, and the same media as mentioned above were setthereon to photograph a subject at f=1.4 and a shutter speed of 1/30sec.

(2) Color CRT displaying

The R, G and B latent images were read by scanning in a similar mannerto form fluorescences corresponding thereto on a CRT, and the resultingimages separated into three colors were compounded on the CRT to obtaina color image.

COMPARATIVE EXAMPLE (a)

A solution of 10 g of a rosin ester resin (Stayberite Ester 10)dissolved in 90 g of n-butyl alcohol was spinner-coated (at 1000 rpm for20 seconds) on a 1 mm thick glass substrate vapor-deposited with 1000 Åthick aluminium, and was thereafter dried at 60° C. for 1 hour toevaporate off the solvent, thereby forming a resinous layer having afilm thickness of 2 μm.

COMPARATIVE EXAMPLE (b)

A 50% solution of a silicone resin (TSR-144 available from ToshibaSilicone and containing 1% of a curing agent CR-15) diluted with xylenewas spinner-coated on a 1 mm thick glass substrate vapor-deposited with1000 Å thick aluminium, and was thereafter dried at 150° C. for 1 hourto evaporate off the solvent and cure the resin, thereby forming asilicone resin layer having a film thickness of 7 μm.

Table 2 shows the charge retainability of the electrostatic informationrecording media of Examples 64 to 72, as expressed in terms of thesurface potentials measured with the lapse of time. The surfacepotentials of the media of Comparative Examples a and b, as measuredwith time, are also tabulated in Table 2.

                  TABLE 2                                                         ______________________________________                                        Estimation of Stability with Time of Internally Accumulated Charges           Ex.  Initial pot.                                                                           Initial pot.                                                                           1-day stor.                                                                           7-day stor.                                                                           30-day stor.                           Nos. (V) (1*) (V) (2*) (60° C., dry)                                                                  (60° C., dry)                                                                  (60° C., dry)                   ______________________________________                                        49   -120     -100      -95    -70     -35                                    a    -105     -105      -40       0       0                                   50   -150     -135     -120    -65     -30                                    51   -130     -120     -100    -60     -25                                    52   -165     -140     -135    -110    -90                                    b    -155     -155     -130    -50        0                                   53    -95      -95      -90    -75     -50                                    54   -160     -150     -150    -140    -115                                   55   -200     -180     -140    -80     -30                                    56   -100      -90      -80    -40     -10                                    57   -150     -120     -110    -80     -45                                    ______________________________________                                         (1*): Initial potentials of the exposed regions before overall exposure.      (2*): Initial potentials of the exposed regions after overa11 exposure.       Note that the photosensitive members used were all PVK  TNF of Example 12     with external application of a voltge of -700 V.                         

EXAMPLE 74! Seventh Electrophotographic Information Recording Medium

A mixed solution of 1 g of a polyester resin (Vylon 200) and 10 g ofchloroform was coated on a 1 mm thick glass substrate by doctor bladecoating, and was thereafter dried at 100° C. for 1 hour to form aninsulating layer of 10 μm in thickness.

Further laminated thereon was amorphous selenium to a film thickness of10 μm at a degree of vacuum of 10⁻⁵ Torr by vapor deposition, therebypreparing an electrophotographic information recording medium as shownin FIG. 6 (a).

EXAMPLE 75!

An ITO transparent electrode is laminated on a 1 mm thick glasselectrode support to a thickness of 1000 Å by sputtering to prepare anelectrode member. This transparent electrode is spaced away from theelectrostatic information recording medium prepared in Example 74through a gap of 10 μm defined by a polyester film spacer in oppositerelation to each other. A DC voltage of 700 V is applied between bothelectrodes with the ITO electrode positively. While the voltage isimpressed, exposure is carried out from the transparent electrode for 1second, using a halogen lamp having a luminous intensity of 1000 luxes.After the completion of the exposure, the voltage was shut off.

In order to release the photoconductive layer from the electrostaticinformation recording medium after the exposure, the recording mediumwas removed out in a dark place. Thereafter, the polyester film 80coated thereon with the adhesive layer 90 was bonded to thephotoconductive layer and then peeled therefrom, whereby thephotoconductive layer 9 was released from the electrostatic informationrecording medium 3. Where the insulating layer after peeling-off wasmeasured in terms of its surface potentials by a surface electrometer, asurface potential of 250 V was obtained on the exposed region and asurface potential of 50 V on the unexposed region.

Similar exposure was carried out, while a resolution pattern film wasbrought in close contact with the back side of the ITO electrode.Thereafter, the selenium layer was released in a similar manner. Afterpeeling-off, the insulating layer was subjected thereon to X-Y axisscanning with a 50×50 μm probe surface for measuring microareapotentials to process potential data of 50 μm units, which were in turndisplayed on a CRT by potential-brightness conversion on an enlargedscale. As a result, resolution patterns of up to 100 μm were confirmedon the CRT.

The electrostatic information recording medium after peeling-off waspermitted to stand at room temperature of 25° C. and a humidity of 35%for three months. Subsequent potential reading by scanning indicatedthat resolution pattern displays quite similar to those just after theexposure were obtained.

EXAMPLE 76!

A photoresist (under the trade name of OFPR-5000 available from TokyoOka) was coated on the electrostatic information recording mediumprepared in Example 74 to a film thickness of 2 μm by spinner coating(at 3000 rpm for 15 seconds). While a chromium mask surface patterned at3 μm pitches in the form of a ckeckerboard was brought in close contactwith the photoresist surface, the obtained recording medium wassubjected to pattern exposure at a dosage of 11.5 mW/cm² and 405 nm for30 seconds. Thereafter, the exposed region was removed off by alkalidevelopment (with an NMD-3 developer) to form a positive type of resistpattern on the recording medium.

Then, the thus patterned recording medium was immersed for 5 minutes in1000 cc of a 10 mole HCl solution mixed with 10 g of zinc powders toetch an amorphous-Se photosensitive layer in a portion not covered withthe resist.

Thereafter, the electrostatic information recording medium was dipped inethyl alcohol for 3 minutes to dissolve the remaining resist pattern.Thus, an electrophotographic information recording medium as shown inFIG. 6 (b) was obtained, in which the photoconductive layer wereseparated into picture element units.

EXAMPLE 77!

With the electrostatic information recording medium of Example 76, anelectrostatic latent image was formed by the resolution pattern exposuremethod used in Example 75.

In Example 75, the selenium layer was peeled off. In this case, however,the deterioration of the latent image was estimated with the seleniumlayer kept intact. As a result, it was understood that the resolvingpower of the latent image, similar to that achieved by peeling-off, wasobtained by the micro-separation of the selenium layer.

EXAMPLE 78!

By the same procedure as in the Example 74, polyester resin of 10 μmthick was coated on aluminum electrode on a glass substrate, on thissubstrate, photoconductive layer having electric anisotropy, consistingof CdS of about 3500 Å thick, was formed by r.f. magnetron sputteringmethod (Ar 30 cc/min.; 1×10⁻² Torr; 50 W) using CdS target, and theelectrostatic information recording medium of FIG. 6 (c) was obtained.

When voltage was applied and exposure was performed by the sameprocedure as in the Example 75 on this electrostatic informationrecording medium, surface potential of 250 V was measured by surfacepotentiometer.

The voltage was applied and exposure was performed by the same procedureas in the Example 75 on this electrostatic information recording mediumusing resolution pattern film during exposure. The potential of theelectrostatic information recording medium was read by potentialscanning reading, as immediately as the information was recorded andafter left at the room temperature of 25° C. and humidity of 30% for 1month. The resolution pattern was not changed from the value immediatelyafter the recording.

EXAMPLE 79!

In Example 75, the recording medium was left in a dark place with theselenium layer kept intact, after pattern exposure. Three days later,its resolution was estimated at room temperature of 25° C. and 35% R.H.by potential reading by scanning. As a result, the initial resolution of100 μm was already found to disappear. In other words, it was found froma uniform potential distribution that charges diffused throughout andalong the film plane.

EXAMPLE 80!

A mixed solution of 1 g of a polyester resin (Vylon 200) and 10 g ofchloroform was coated on a 1 mm thick polyester film vapor-depositedwith 1000 Å thick aluminium by doctor coating, and was then dried at100° C. for 1 hour to form a 10 μm thick insulating layer.

A mixture composed of 10 g of ZnO powders, 0.1 g of bromophenol blue and100 g of ethyl alcohol was then pulverized and kneaded together in aball mill. The obtained product was thereafter introduced into a vessel,and the alcohol was evaporated off by drying to prepare ZnO powdershaving bromophenol blue adsorbed thereon. Subsequently, a mixture of 10g of such ZnO powders having bromophenol blue adsorbed thereon, 10 g ofpolycarbonate (Pan-Light available from Teijin) and 20 g of ethylcellosolve was dispersed with an ultrasonic stirrer to prepare aphotosensitive liquid for coating. This liquid was coated on the aboveinsulating layer with a blade coater (4 mm) and dried at 100° C. for 1hour, whereby a photoconductive layer having a film thickness of 10 μmwas laminated thereon to make a dispersed type of electrostaticinformation recording medium, as shown in FIG. 6 (d).

EXAMPLE 81! Electrostatic information recording medium in whichelectrostaticinformation was changed to positional information

A solution of 10 g of a rosin ester resin (available under the tradename of Stayberite Ester 10) serving as a thermoplastic resin and 1 g ofa hydrozone derivative (CTC-191 available from Anan Koryo) serving as ancharge transport material, both dissolved in 50 g of tetrahydrofuran,was spinner-coated at 1000 rpm for 90 seconds on a glass substratevapor-deposited with 1000 Å thick aluminium. The coated film was driedat 60° C. for 1 hour to evaporate off the solvent. As a result, auniformly coated film having a film thickness of 2 μm was formed.

Amorphous selenium was laminated on this medium by vapor depositionunder the following conditions.

The medium is first fixed to a substrate holder within a vacuum chamber,while the glass side comes in close contact therewith. The substrateholder is heatable (by means of a heater). During vapor deposition, thesubstrate medium is heated to 100° C. The vapor deposition of seleniumwas carried out at a degree of vacuum as low as 0.1 Torr by ordinaryresistance heating. As a result, an electrophotographic informationrecording medium was obtained, in which selenium was formed to a depthof 0.1 μm in the rosin ester layer in the form of microparticles havinga mean particle size of about 0.5 μm.

EXAMPLE 82!

Ten (10) g of an AS resin (Stylac ASL-76 available from Asahi Kasei)were used in place of the rosin ester resin employed in Example 81 toobtain an electrostatic information recording medium in otherwisesimilar manners.

EXAMPLE 83!

Ten (10) g of a terpenic resin (Picolastic A-75 available from RikaHercules) were used in place of the rosin ester resin employed inExample 81 to obtain an electrostatic information recording medium inotherwise similar manners.

EXAMPLE 84!

Seven (7) g of a terpenic resin (Picorite A-115 available from RikaHercules) were used in place of the rosin ester resin employed inExample 81 to obtain an electrostatic information recording medium inotherwise similar manners.

EXAMPLE 85!

Five (5) g of a terpenic resin (Picorite S-70 available from RikaHercules) were used in place of the rosin ester resin employed inExample 81 to obtain an electrostatic information recording medium inotherwise similar manners.

EXAMPLE 86!

In Example 81, low-vacuum vapor deposition was carried out using as thematerial to be vapor-deposited gold in place of selenium. As a result,an electrically conductive particle type of charge retaining medium wasobtained, in which gold microparticles having a mean particle size of0.2 μm was formed 0.1 μm below the surface of the Steberite resin in theform of a single layer.

EXAMPLE 87!

The single layer organic photosensitive member (PVK--TNF) of Example 16was positioned in opposition to the electrostatic information recordingmedium 3 prepared in Example 81 through a polyester film spacer having afilm thickness of 10 μm. A DC voltage of -700 V was impressed betweenboth electrodes with the photosensitive member negatively and theresinous layer positively.

While the voltage was applied, exposure was performed from thephotosensitive member using as the light source a halogen lamp having aluminous intensity of 1000 luxes. As a result, a surface potential of-150 V was obtained on the exposed region.

After the completion of the exposure, the recording medium was removedout for overall exposure, whereby negative surface charges weretransferred into the particles. Thereafter, the recording medium washeated to 80° C. by resistance heating, resulting in the chargeaccumulated particles passing into the resin.

After this electrostatic information recording medium was left for 7days, positive charge of +450 V were imparted on the overall surfacethereof by corona charging. Just after the overall exposure, its surfacepotential was read. As a result, the exposure pattern could bereproduced on a CRT.

The opposing electrode was placed face-to-face to the electrostaticinformation recording medium using polyester film of 10 μm thick as aspacer, and positive electric charge with voltage of 750 V were impartedon the overall surface of the electrostatic information recording mediuminstead of corona charging with the opposing electrode as positive andelectrostatic information recording medium as negative. By the sameprocedure as in the corona charging, the exposure pattern could bereproduced on CRT.

Next, the same exposure was performed with the resolution pattern filmclosely fit on the photosensitive member glass substrate duringexposure. Thereafter, the electrostatic information recording medium wassubjected to X-Y axis scanning with a 50×50 μm probe surface formeasuring microarea potentials to process potential data of 50 μm units,which were in turn displayed on a CRT by potential-brightness conversionon an enlarged scale. As a result, resolution patterns of up to 100 μmwere confirmed on the CRT.

In electrophotographic image recording, the recording medium wassubjected to pattern exposure with a resolution pattern film andheat-developed in a similar manner as mentioned above, after uniformelectrification to -600 V. It was then found that a resolution patternof 200 μm was only confirmed on a CRT during reproduction due to theoccurrence of frost.

For alternative exposure, a subject was photographed with an ordinarycamera at an impression voltage of -700 V, an exposure f=1.4 and ashutter speed of 1/60 sec. outdoors in the daytime. After the exposure,the recording medium was corona-electrified and exposed to light on itsoverall surface. This recording medium was subjected to X-Y axisscanning with a 50×50 μm probe surface for measuring microareapotentials to process potential data of 50 μm units, which were in turndisplayed on a CRT by potential-brightness conversion on an enlargedscale. As a result, imaging having gradiation was found to occur.

Color images were photographed in the following manners.

(1) Prismatic three-plane splitting

As illustrated in FIG. 12, the R, G and B filters were disposed on threeplanes of a prism and the same media as mentioned above were set thereonto photograph a subject at f=1.4 and a shutter speed of 1/30 sec.

(2) Color CRT displaying

The R, G and B latent images were read by scanning in a similar mannerto form on a CRT fluorescences corresponding thereto, and an imageseparated into three colors was compounded on the CRT to obtain a colorimage.

EXAMPLE 88! Protective Film-Laminated Electrostatic InformationRecording Medium

The single layer organic photosensitive member (PVK--TNF) prepared inExample 16 is superposed on the electrostatic information recordingmedium prepared in Example 14 (a) in opposite relation through apolyester film spacer having a film thickness of 10 μm. A DC voltage of-700 V is applied between both electrodes with the photosensitive membernegatively and the charge retaining layer positively. While the voltagewas impressed, exposure was carried out from the photosensitive memberfor 1 second, using as the light source a halogen lamp having a luminousintensity of 1000 luxes. After the exposure, the voltage was cut off.

Ten (10) mg of dimethyl silicone oil (having a viscosity of 10000 cpsand available from Toshiba Silicone) were added dropwise onto thesurface of the charge retaining layer in which an electrostatic imagewas recorded. Further laminated on the charge retaining layer was a 20μm thick polyester film to bring them in close contact with each other,thereby forming a protective film.

Charge retainability

After the above electrostatic image had been recorded, a surfacepotential of -180 V, as measured with a surface electrometer, wasobtined on the charge retaining layer with no protective film laminatedthereon. On the other hand, the unexposed region was found to have asurface potential of -40 V. As a result of further measurement ofsurface potentials from above the protective film, there was againobtained a surface potential of -180 V similar to that measured on theexposed region with no protective film laminated thereon.

EXAMPLE 89!

In place of the silicone oil used in Example 88, silicone rubber (TSE326 available from Toshiba Silicone) was coated on a 20 μm thickpolyester film with a doctor blade, and was then dried at 100° C. for 1hour to form a 2 μm thick film. This protective film was laminated onthe surface of the charge retaining layer in which the electrostaticimage was recorded by the same way as Example 88. From the measurementof the surface potential of that layer, it was found to have similarcharge retainability as obtained with the silicone oil.

EXAMPLE 90!

A 1 mm thick glass support was vapor-deposited with aluminium to athickness of 1000 Å, on which polyp-xylene was then vapor-deposited as acharge retaining layer, thereby obtaining an electrophotographicinformation recording medium.

A solution of a fluorine-containing resin (available from Asahi Glass)dissolved in a fluorine base solvent was spinner-coated on the surfaceof the charge retaining layer to which a surface potential of -100 V wasimparted, thereby forming a 3 μm thick protective layer. The measurementof surface potentials from above this protective film indicated that asurface potential of -100 V similar to that measured with no protectivefilm laminated was obtained.

EXAMPLE 91!

With a roll coater, a 30% solution of Stayberite Ester 10 (availablefrom Rika Hercules) dissolved in monochlorobenzene was spread to a drythickness of 7 μm on the surface of a 6 μm thick polyester film(available from Toray) one side of which had been release-treated with asilicone base release agent, thereby preparing a film for hot-melttransfer.

The electrostatic information recording medium prepared in Example 14(a) was electrified to a surface potential of -100 V, and the above filmfor hot-melt transfer was then transferred thereon as a protective filmwith a heat sealer by a heat roll heated to 60° C.

Surface potential was measured from above this protective film. As aresult, it was confirmed that a surface potential of -100 V similar tothat measured with no protective film laminated was obtained and, hence,the protective film could be formed by hot-melt transfer.

EXAMPLE 92!

FIG. 67 is a view showing changes-with-time of the charge retainabilityof the electrostatic information recording medium of Example 90. In FIG.67, ∘ and □ each refer to the charge retainability of the recordingmedium with no protective film laminated thereon; x and Δ each stand forthe charge retainability of the recording medium having the protectivefilm laminated thereon; ∘ and x each denote the results of measurementof the recording medium allowed to stand at room temperature and 50%humidity; and □ and Δ each represent the results of measurement of therecording medium permitted to stand at a temperature of 40° C. and ahumidity of 95%.

As can been seen from this figure, remarkable improvements areintroduced in charge retainability by the provision of the protectivefilm. Referring to the results of measurement with the electrostaticinformation recording media allowed to stand at room temperatrue and 50%humidity, the surface potential of the recording medium (shown at x)with the protective film layer laminated thereon suffered from no orlittle attenuation as compared with that of the recording medium (shownat o) with no protective film layer laminated thereon, even after thelapse of one month. Referring then to the results of measurement withthe electrostatic information recording media permitted to stand at atemperature of 40° C. and a humidity of 95%, the surface potential ofthe recording medium (shown at □) with no protective film layerlaminated thereon showed a 45% attenuation, but that of the recordingmedium (shown at Δ) having the protective film layer laminated thereonunderwent a barely about 35% attenuation, after the lapse of one month.

It is to be understood that when the medium having no protective filmlaminated thereon was immersed in water, the charge was completely lost,while whereas the protective film-laminated medium was immersed inwater, the potential could not be read from above the protective film asa consequence of water immersion; however, the original potential wasobserved with no change in resolution, when the protective film wasreleased from the medium to measure its surface potential.

EXAMPLE 93! Electrostatic information recording medium in which audioinformation was recorded.

The amorphous silicon (a-Si) photosensitive member of Example 17, theelectrostatic information recording medium of Example 14 (a) and a glasssubstrate, put one upon another, was incorporated in a camera with theelectrodes outside. In this case, a void is provided between thephotosensitive member and the recording medium by disposing a 10 μmpolyester film spacer around its region except for the region to beexposed to light.

A voltage of 700 V was then applied with the photosensitive member'selectrode negatively and the recording medium positively. In that state,an optical shutter was released at an exposure f=1.4 and a shutter speedof 1/60 sec., or a voltage was impressed for 1/60 sec. at an exposuref=1.4 with the shutter kept open, to photograph a subject outdoors inthe daytime.

The camera has a microphone, an amplifier and an acoustic-opticalmodulator built-in to convert a sound into electrical signals when thesubject is photographed. In addition, the camera has a semiconductorlaser (780 nm: 1 mw) built-in so as to record audio signals in therecording medium in the form of electrostatic charge potential. Theintensity of laser beams is then subjected to analog recordingcorresponding to the audio signals in combination with the abovemodulator. The laser beams are scanned by a polygonal mirror on timebasis and recorded in some area of the recording medium in the form ofpotential signals.

For five seconds before and after the shutter was released, the audioinformation was actually converted to optical signals to record them inthe recording medium in the form of potential information. As a result,the audio information during photographing was recorded between 0 V and-70 V in an analog manner separately from image information.

After the exposure and the application of voltage were both put off, theelectrostatic information recording medium was removed out in a dark orbright place for imaging (1) on a CRT by microarea potential reading and(2) by toner development.

In (1), the recording medium was subjected to X-Y axis scanning with a50×50 μm probe for measuring microarea potentials to process potentialdata of 50 μm units, which were then imaged on a CRT bypotential-brightness conversion. Formed on the recording medium wereanalog potential latent images from a high 200 V potential of theexposed region to a low 0 V potential of the unexposed region, whichcould be developed on the CRT with a resolution of 100 μm.

In (2), the removed recording medium was immersed in a negativelycharged wet toner (black) for 10 seconds, whereby a positive image wasobtained. The resolution of the obtained toner image was as high as 1μm.

Color images were photographed in the following manners.

(1) Prismatic three-plane splitting

As shown in FIG. 12, the R, G and B filters were disposed on threeplanes of a prism, and the above media were set thereon to photograph asubject at f=1.4 and an shutter speed of 1/30 sec.

(2) Color CRT displaying

The R, G and B latent images were read by scanning in a similar mannerto form on a CRT fluorescences corresponding thereto, and imagesseparated into three colors were compounded on the CRT into a colorimage.

(3) Toner development

The R, G and B latent images on the recording medium subjected to colorseparation and exposure were developed with negatively charged C (cyan),M (magenta) and Y (yellow) toners into toner images. Before the tonerwas dried out, paper was placed on the medium on which the cyan tonerimage was formed, and was then positively corona-charged. Subsequentrelease of the paper resulted in the transfer of the toner imagethereon. While the images were in alignment, the magenta and yellowtoners were successively transferred to the same place for compounding.As a result, a color image was formed on the paper.

EXAMPLE 94! Preparation of ROM Type of Electrostatic Charge RecordingCard

As shown in FIG. 61, a 0.8 mm thick vinyl chloride sheet (85×55 mm) wasused as the card substrate 4, and a rectangular recess for receiving theelectrostatic charge recording member 3 is formed in the upper side ofthe card substrate. Then, a bonding agent is applied on a supportsurface of the recording member 3 in which information is recorded, andthe member 3 is embedded in the recess with the charge retaining layerexposed to view, followed by pressing for integration. Finally, thepolyester film 20 was provided on the card substrate to prepare anelectrostatic charge recording card.

EXAMPLE 95! Preparation of DRAW Type of Electrostatic Charge RecordingCard

As illustrated in FIG. 62, a vinyl chloride sheet (85×55 mm) was used asthe card substrate 4, and a recess for receiving the electrostaticcharge recording member 3 is formed in the upper side thereof. Thatrecess is provided through its bottom with a hole leading to the backside of the substrate. On the other hand, the electrode 13 is providedon its back side with an exposed electrode portio 6 and an electrode byintegral molding, followed by the lamination of the insulating layer 11.Thereafter, the electrostatic charge recording medium was placed andpressed in the recess in the card substrate 4 with the electrode portion6 being exposed on the through-hole, thereby making the recording mediumintegral with the card substrate. A silicone rubber film was sticked tothe surface of the recording medium (although not illustrated).

How to record information in this DRAW type of electrostatic chargerecording medium is illustrated in FIG. 63. After the protective filmwas first released off, a voltage of 700 V was applied between bothelectrodes 7 and 13, as illustrated in FIG. 63 (a), while exposure wascarried out for 1 second using a halogen lamp of 1000 luxes to recordthe information on the surface of the insulating layer. Thereafter, theprotective film was again sticked in place. As a result of themeasurement of surface potentials from above this film, it was foundthat the image information bearing charges were satisfactorily retainedand did not attenuated at all after the lapse of three months.

What we claim is:
 1. An electrostatic information recording medium comprising;(a) an electrode layer having a specific resistance of 10⁻⁶ Ω·cm or less; (b) an electric charge retaining layer laminated to the electrode layer, said layer being fabricated of a macromolecular material having a glass transition temperature higher than that of the environmental temperature, a water absorption ratio of 0.4 wt % or less and a specific resistance of 10⁻¹² Ω·cm or more.
 2. An electrostatic information recording medium as set forth in claim 1, wherein macromolecular material is a resin containing fluorine.
 3. An electrostatic information recording medium as set forth in claim 1, wherein macromolecular material is polyester resin.
 4. An electrostatic information recording medium as set forth in claim 1, wherein macromolecular material is polyparaxylylene.
 5. An electrostatic information recording medium as set forth in claim 1, wherein macromolecular material is polyethylene naphthalate.
 6. An electrostatic information recording medium as set forth in claim 1, wherein macromolecular material is methylphenyl silicone resin.
 7. An electrostatic information recording medium as set forth in claim 1, wherein macromolecular material is polyimide resin.
 8. An electrostatic information recording medium as set forth in claim 1, wherein the electric charge retaining layer consists of mono-layer film or built-up layers film with insulating property.
 9. An electrostatic information recording medium as set forth in claim 1, wherein the electric charge retaining layer is optical electret.
 10. An electrostatic information recording medium as set forth in claim 1, wherein the electric charge retaining layer is thermal electret.
 11. An electrostatic information recording medium as set forth in claim 1, wherein the electric charge retaining layer consists of an electric charge retaining reinforced layer combined with the insulating layer with film thickness not to admit the injection of electric charge.
 12. An electrostatic information recording medium as set forth in claim 11, wherein an electric charge retainability reinforced layer is formed on an electrode and an insulating layer with film thickness not to admit the injection of electric charge is formed.
 13. An electrostatic information recording medium as set forth in claim 11, wherein an insulating layer with film thickness not to admit the injection of electric charge is formed on an electrode and an electric charge retainability reinforced layer is formed.
 14. An electrostatic information recording medium as set forth in claim 11, wherein the electric charge retainability reinforced layer consists of inorganic insulating film, organic macromolecular insulating film, monolayer film or built-up layers film and the film thickness thereof is within the range of 10-1000 Å.
 15. An electrostatic information recording medium as set forth in claim 11, wherein the film thickness not to admit the injection of electric charge is 100 Å or more.
 16. An electrostatic information recording medium as set forth in claim 1, wherein the electric charge retaining layer consists of an insulating resin layer containing the photoconductive or electrically conductive particles and is capable to accumulate the electric chare in said particles.
 17. An electrostatic information recording medium as set forth in claim 16, wherein the photoconductive or electrically conductive particles are present in single layer or multiple layers in the vicinity of the interior surface of the insulating resin layer.
 18. An electrostatic information recording medium as set forth in claim 16, wherein the photoconductive or electrically conductive particles are dispersed in the insulating resin layer and are laminated on the insulating resin layer, which is piled up on the electrode.
 19. An electrostatic information recording medium as set forth in claim 16, wherein the photoconductive or electrically conductive particles are dispersed in the insulating resin layer and are laminated on the electrode.
 20. An electrostatic information recording medium as set forth in claim 1, wherein the electric charge retaining layer consists of photoconductive or electrically conductive particles laminated in single layer or in multiple layers on the insulating layer, the electric charge transport layers are sequentially laminated on said particle layer which primarily transport one polarity part of the electric charge and are laminated on the electrode from the said of insulating layer.
 21. An electrostatic information recording medium as set forth in claim 1, wherein the electric charge retaining layer consists of photoconductive layer detachably laminated on the insulating layer and it is laminated on the electrode from the side of insulating layer.
 22. An electrostatic information recording medium as set forth in claim 1, wherein the electric charge retaining layer is such that insulating layer and photoconductive layer are sequentially laminated, said photoconductive layer is made of the substance having orientation in thickness direction and is laminated on electrode from insulating layer side.
 23. An electrostatic information recording medium as set forth in claim 1, wherein the electric charge retaining layer is such that insulating layer and photoconductive layer are sequentially laminated, and said photoconductive layer is made of the substance of photoconductive particle dispersion type and is laminated on electrode from the insulating layer side.
 24. An electrostatic information recording medium as set forth in claim 1, wherein electrode is supported by support member, and electric charge retaining layer is laminated on electrode.
 25. An electrostatic information recording medium as set forth in claim 24, wherein support member is made of flexible base material.
 26. An electrostatic information recording medium as set forth in claim 24, wherein support member, electrode, and electric charge retaining layer are transparent.
 27. An electrostatic information recording medium as set forth in claim 1, wherein the protective film is laminated on the electric charge retaining layer to increase the electric charge retaining property.
 28. An electrostatic information recording medium as set forth in claim 27, wherein the protective film is the insulating plastic film.
 29. An electrostatic information recording medium as set forth in claim 27, wherein the protective film is formed by coating the insulating plastic solution.
 30. An electrostatic information recording medium as set forth in claim 27, wherein the protective film is formed by the melting transfer of the insulating melting plastics.
 31. An electrostatic information recording medium as set forth in claim 1, wherein a part of the information recording region is the audio information recording region and audio information is recorded.
 32. An electrostatic information recording medium with audio information recorded as set fort in claim 31, wherein the audio information recording region is at the periphery of the electrostatic information recording medium.
 33. An electrostatic information recording medium as set forth in claim 1, wherein the electric charge retaining layer is laminated on the electrode and the electrode is laminated on the card base material.
 34. An electrostatic information recording medium as set forth in claim 33, wherein the surface of the electric charge retaining layer is exposed and embedded in the card base material or the electric charge retaining layer is attached and laminated on the card base material.
 35. An electrostatic information recording medium as set forth in claim 33, wherein the electric charge retaining layer is laminated with or without the recorded information.
 36. An electrostatic information recording medium as set forth in claim 33, wherein the recording form of the information is either the electric charge or the toner by toner development.
 37. An electrostatic information recording medium as set forth in claim 33, wherein the electrode is partially exposed and laminated at appropriate point of the card base material. 